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Option 1: World trade center, Recommended
From the center (Slovenska Cesta, Dunajska Cesta), take a bus number 6 (direction Črnuče), 8 (dir. Brnčičeva) or 11 (dir. Ježica) and get off at the stop "Smelt", close to the WTC tower. Walk a bit further on towards the motorway and turn right at the crossroads. Right after the fountain you will see the road forking, the left lane going down to the motorway, the right lane going higher up. Stand with your sign in the middle between the two lanes, or on the pavement next to the parking place entrance. Even though the first option might look a bit strange, this is the most common spot and it's easy for drivers to see you and there's enough space for one car to safely stop there.
Option 2: Letališka
Take bus no 27 towards "Letaliska" and get out at "Jarše". Continue following "Šmartinska cesta" about 400 meters and turn right from the traffic lights. There is a bus stop right after. Most of the cars passing now are going towards the highway. You can also take bus no 2 to "Nove Jarše" from Southern part of Slovenska cesta. The last stop is the mentioned hitchhiking spot.
Direction north-west there is the motorway E61/A2 towards Kranj through the Karawanken Tunnel (Slovenian: Predor Karavanke) or over the pass over the border to Villach (slov.: Beljak) in Austria and further on on the Tauern-motorway to Salzburg and over to Germany. It is the way that is used by most of those numerous Germans that go to the Croatian coast for hollidays.
This motorway E61/A2 starts from the Ljubljana bypass. The best way to join this motorway is from the street Celovška cesta, at the bus stop Šentvid (stand in the corner before the bus stop!!). Get there by bus number 1 (direction Vižmarje), 25 (dir. Medvode), or 8 (dir. Gameljne) from the city centre. If people who pick you up don't go as far as you like, you can get a lift as far as the first "Petrol" gas station on the highway (17km away) or the former toll station Torovo and keep hitchhiking there. There is also a petrol station at the Radovljica-exit (right before Bled) which is useful for getting into Austria. Another option is to get dropped at ~25km from Šentvid, there's a great hitchhiking spot here on a ramp where there's enough room for a car to stop (GPS 46.267470, 14.339623).
Option 1: Highway entrance Dolgi Most, Recommended
From the city centre (Dunajska cesta, Slovenska cesta) take the bus number 6, 1, 1D (direction Dolgi most - last stop) or 6B (dir. Notranje gorice), to bus stop "Dolgi Most". You will be dropped off on a large parking lot right next to a motorway bridge. On the opposite side of the road, there is a busy motorway entrance with a great hitchhiking spot where cars can easily see you and stop safely. Slovenians use this ramp to go to the seaside, so waiting times should not be too long.
If your destination is Venice or further, the easiest way is via Nova Gorica (town on the walkable distance from Gorizia, Ita): use sign GO and ask to be dropped at the service area on the border. For Trieste it doesn't work well with TS sign - best option might be to use Koper sign and then ask the driver to drop you off at Kozina exit (go right in the crossroads after toll booths). It's only 3 km from the border and on the main Rijeka-Trieste road.
If your destination is Rijeka, take also rides going to Postojna or further west. Get out at Postojna exit and walk across the highway from there (use the bridge). There is a good spot to hitchhike southwards just few hundred meters after the bridge.
Option 2: Rest stop Barje - North (Sever)
Catch bus 9 to bus stop "Pot Na Rakovo Jelšo" and go straight to direction where bus went follow Cesta Dveh Cesarev street (dont turn the left side where bus went after 100 metres). Asphalt road will bring you to place where you can see fuel station search tiny tail to it! There is shower in fuel station price 3 eur and places for wild camping around.
Option 3: Fuel station on the road to highway
Near the crossing of streets: "Pot Na Rakovo Jelšo" and "Barjanska Cesta" there is a fuel station with a lot of cars heading towards Koper.
Southeast towards Novo mesto, Zagreb (Croatia)
Option 1: Rest stop Barje - South (Jug)
This service area is on the Ring around Ljubljana and is very well-served by a lot of long-distance drivers. To get there take a bus number 1 or 1B in direction of "Dolgi most" from the center. Get off the bus on the stop "Mestni Log" and walk back in the direction of the highway. When you reach the overpass look for a very small and steep pathway on your right, starting next to the overpass. Descend down to the fence, turn right and walk a few metres untill you reach an unlocked door. When you're on the other side of the fence, you should already be able to see the rest stop. Follow the pathway for another 100 m or so and there you are. There is a shower for 3€ and places for wildcamping around.
- MartinJ888 August 2022: Works very well. The door is still unlocked! Took us about 1 hour to get a ride, asking people.
Option 2: Highway entrance Barjanska cesta
Catch bus 9 in direction of "Barje" from the center or the train station and exit on the final stop "Barje". You can hitchhike next to the parking lot or walk down the "barjanska" street and try to find a better place. That's the entrance people from Ljubljana would use to enter the highway going south, so this spot might be less suitable for long distance picks, but perfect to get you to Novo Mesto.
Option 3: Highway entrance Rudnik
Not many cars go in this direction, and the ones that do usually do not enter the motorway here - this on-ramp mostly serves inter-urban traffic, so you might have to wait a bit longer. From the city centre take a bus line 3 in direction of "Rudnik", and get off at the final stop. In front of you there will be the motorway entrance. Cross the street and on the side of the on-ramp road, on your left, you will see a small asphalt surface where all the cars pass, and there you can stand and hitchhike easily. Pay attention that you're hitchhiking on the highway entrance (the left turn) and not on the old road (Dolenjska cesta), which is continuing straight ahead. Drivers going to Kočevje and Ribnica use this entrance.
The best option in a walkable distance from the city centre would be park Tivoli. It is huge so you can easily find a good place to hide and set up your tent somewhere. People often drink there in the evening so it might be a good idea to sleep in or at least close to the forest, so nobody will bother you.
Another place is up the castle, close to the antena. Just follow the path going away from the castle entrance and it will take you to a small meadow and a small forrest. There is a bigger chance to be spotted here.