Hitching in and around
If you're coming from the West, East or North and want to proceed in one of these directions, there is a main road that connects two roundabouts in the West and the East of the center which are great jump-off points. It's possible to hitch on this road even though it's within the city. For more details, see below.
If you get dropped off in the centre and wish to hitchhike onward, there are plenty of buses and trolleybuses and local people can tell you which to take. Besides Russian and Ukrainian, Romanian and German are widely spoken.
Northwest towards Ivano-Frankivsk (H10), north towards Ternopil' (M19)
From the central train station (vokzalu stantsia) you have to follow the street to the northwest for about 2km. Turn left at the roundabout after crossing the river. Directly after the roundabout there is a small bus terminal on your right and plenty of local people trying to get a lift or just waiting for a marshrutka.
The road splits into the H10 towards Ivano-Frankivsk and the M19 towards Ternopil' at the village Mamaivtsi which is 8km further. Here you can find a great spot for going to Ternopil': a huge roundabout after which you can stand right before a railroad crossing where all drivers have to slow down if they don't want to wreck their car. Street lighting for dark nights inclusive.
n0id and M. first tried to hitch next to the locals at the bus station, but soon walked a bit further and got a lift to Mamaivtsi. Here they also had the company of a few locals coming and leaving by flagging down a ride. At around 10pm there was not too much traffic, but trucks passed by once in a while and finally one, going all the way to Poland, stopped.
East towards Moldova
If you're coming from the West or North and transiting, don't go into the city. Have yourself dropped off at the first roundabout described below.
From the central train station (vokzalu stantsia), follow the street to the northwest for about 2km. After crossing the river, you'll get to a roundabout. Follow the signs saying Chisinau, and you'll get onto a very long straight boulevard that after 9km and one bend leads to another roundabout which is a perfect spot for finding a lift to Novoselica and onto Moldova. The recommended thing to do is to hitch on the beginning of the long straight boulevard. A sign would help greatly. Zenit walked 3.5km in August 2011 until the train crossing and got a lift to the roundabout from there.
South towards Suceava (RO) (M19)
To leave Chernivtsi towards Romania, find a stop of the trolley bus #3 (ask any bus driver). From the center (Ulica Rosskaja), you could for example take bus #202 and ask your driver to advise you. Get off trolley bus #3 at the last stop and walk down the road a few hundred meters. There's not a lot of traffic, and Zenit got two local lifts before a Russian truck headed to Greece picked him up. The road enters Romania at the Siret-Porubnoe border crossing.