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|Major roads:||A1, E70, E61|
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Trieste is a city in the very east of Italy.
Most traffic going to Rijeka is passing a small village called Basovizza. You can take the bus #39 to get there. The bus starts at the main rail station inside the city, passing the university, then uphill. When the bus is leaving the main road, then it is the right time to get out. Go back to the road and start hitchhiking from there. It's an average place there, because it is behind a curve, but you will be seen soon enough to get away.
If you can get a short ride of about 5km to the former border with Slovenia, take it. There is a small petrol station and some restaurants, drivers have a better opportunity to stop here, so, you can stand next to the main road and tramp or talk with the people who stop to take gas. My friend and me got a direct ride to Rijeka in about half an hour.
Edit: since this road goes through Slovenia it's pretty easy to catch a ride for Ljubljana too.
Take a tram to Opicina (cost 1.35eur, February 2015), which is a town almost at the border. The main village road becomes the road to the border, getting out of town there are places where vehicles can stop. Recommended place is in front of NLB bank at the end of the town and where cars can stop easily. Just after the border there is a gas station on the motorway, or you can stand by the old road. (December 2013: The Tram is broken since September 2012, Take the bus 2/ ). (August 2014 : You can take the bus 42 to the end and there you are less than 300m from the border, and there is a safe place to hitchhike from and room for cars to stop by.)
Or you can ask at the train station for a bus to Sežana,ask for timetable because there aren't many buses per day. Once you are in Sežana walk down a little through the city until you see the signal of Ljubljana. You'd better hitch hike before getting in the the highway, there are not many cars but usually one of that few will stop.
Take a bus that goes to Aquilinia, for example bus #20 departing from the city centre, direction Muggia. Get off at the first stop in Aquilinia, which is more or less the first stop after passing an industrial district. Walk towards the second stop (if you aren't already there). The second stop is located right after a traffic light and a zebra crossing. In front of you you will see a blue sign which encourages drivers to slow down. A couple of hundred meters further the roads splits, one can either enter the motorway or drive towards Muggia. Probably good to have a sign (KP for Koper). Average waiting time 45 minutes (Italy is not very hitchhiking friendly).
Your best option is to get to a Area Servizio (petrol station) on the motorway. The easiest way to do that is to take bus line 51 from Trieste bus station (around 2 Euro), and get out some 30 minutes later at the village of Sistiana in front of the big supermarket "Cooperative Sociali" ex Bar Duino Bianco. Keep walking on the same direction the bus is going for about 400 meters, when you will reach an Agip gas station on the statal road. The back of this gas station is connected with the rest area on the highway, direction Slovenia. To go direction Venice, just use the underground tunnel connecting the two rest areas.
One other option is to take bus #36 from the center of Trieste. It follows the road along the coast and this road (Viale Miramare) is the one leading to the motorway. Get out of the bus at the stop before the last one. There's no ideal spot on this road but if you walk a bit more on this road you can find a couple of acceptable places. You will need some luck though but it's probably your best bet. You should probably ask to get dropped at a petrol station on the motorway since you probably won't find a straight ride to Venezia.
Val [] had no Internet to check here and was only dropped off by accident in the center (the driver's misunderstanding). Therefore, he asked the center the fastest way to the highway and closest with the bus and everybody told him from the train station take the bus to the airport (around 4€, Aug.2014) and ask the driver. The bus is easy to find if you ask for it. Get off at the last stop and walk back to the round about. You can either wait there or just walk to the saver spot to be taken fast along the way until you reach 3km later the peage to the highway.
There is sometimes a controller but when some anonymous hitchhiker got controlled he just told the controller that he thought he would be able to buy a ticket from the driver (which is not possible) and the conductor just walked away. This is just his own experience though and maybe you won't be lucky. If you speak Italian, don't show it to the conductor!
There is a Nomad Base in Trieste 10 minutes walking from the center where you can stay for free. Mobile/whatsapp +39 3895337956
You can sleep in Barcola - a big park on the coast about 5 km far from city center. You can reach Barcola with a bus C from the railway station or with a tram from Obedram (tram station not far from center). You can also sleep in a tent there: in the morning there are many people coming to swim, but nobody pays attention to the tent. If it's getting late and you didn't find a place for the night, the train station is also a good option. Just find a quiet spot, between the others that already did, and you'll get a rather quiet sleep for the night; Until 6:20, when the guard came and woke everybody up, I wasn't bothered at all. WARNING: DO NOT SLEEP AT BARCOLA! OR IF YOU REALLY HAVE TO: DO NOT PUT A TENT THERE! Barcola is patrolled by Carabinieri every morning. One I had to sleep there (it was too late to get anywhere else). Although I didn't put a tent and made my place look like early beachgoer, in the morning I was woken up by the police. Fortunately, managed to get only with admonishment, mainly because I didn't have a tent.
If you want to sleep near the see, go near to Miamare castle. There are some flat concrete spots, where you can safely sleep. Keep close to the road so you won't be visible from the road. And be warned: the Carabinieri outpost right above you! Thus I would not recommend putting a tent, but I found it quite comfortable to sleep just on the inflated mattress there it during the summer.
The other option are hills above Trieste. Take the bus 2 and go near to Obelisco on the top. You can also take a bus 38, but you'll have to walk a little up from the last stop. There is a tap with drinkable water near the Obelisco. Go to the Obelisco, you can put a tent behind trees near the Obelisco. Also you may take dirt road that does not go up and you will find some places near the road (with nice view on the bay).