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Edirne is a border town in the north-west of Turkey.
Northwest towards Bulgaria
In Edirne there are lots of dolmus (minibuses) which go to the Kapitan Andreevo-Kapıkule border crossing. You can stop them on the main street leading towards the border. These take you right to the border crossing and cost 2.5 lira (EUR 0.85). But if you express that you're hitchhiking, it's possible that you'll get a free lift.
User jopoking hitched twice by going directly on the big highway that is passing by the city. The highway fence has lots of holes and unrepaired parts so you can access the street quite easily. Even without actual hard shoulder a truck and the next day a car stopped for me. Just pay attention if there is more traffic.
West towards Greece
The Pazarkule border crossing is at walking distance from downtown Edirne. Walk to the direction of Karaağaç (pronounced kaa-raa-aa-aach). Signs aren’t very common, so you may have to ask someone. Don’t walk in the direction of Pazarkule indicated by signs out of the city centre, as they actually direct vehicles to a longer road around the city, but you may thumb on them. After walking for about 25-30 minutes, you’ll pass two long and historical bridges very near each other (spanning over the Tundza/Tunca and Maritsa/Meriç respectively) and then soon you’ll see a sign showing the direction to Batı Trakya (Western Thrace) and Selanik (Thessaloniki). At that spot, you are about 4 km away from the checkpoint and you may either keep walking or start thumbing. Unlike the Ipsala checkpoint (another border crossing between Turkey and Greece, some hundred kilometres to south), it is allowed to cross this checkpoint on foot. Traffic is very low, so the best is to ask drivers for a ride right at the Greek check point.
South towards Istanbul
It's no problem to walk onto the motorway and try hitchhiking along the hard shoulder. Just watch out for drivers overtaking cars on the right instead of the left side.
It is no problem at all to put up your tent in the park in front of the Selimiye Mosque. We were actually encouraged to do so while asking the locals for a place to sleep.