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Vorarlberg is one of the federal states of Austria. It is situated on the right bank of Rhine river, at the eastern end of the Lake Constance. It borders Germany on the North, Switzerland and Lichtenstein on the West and the Austrian federal state of Tyrol on the East, separated by Arlberg mountain massif.
The language locals speak belongs to the family of Allemanic dialects of the German language. Everybody speaks high German (hochdeutsch) and the vast majority of people speak some degree of English as well.
From North Tyrol
There is quite a big petrol station Shell with a restaurant in Hohenems. It serves both directions. You can get to Hohenems by bus from Dornbirn (2 EUR) or train going between Bregenz and Feldkirch (4 EUR from Bregenz), or hitchhike. The petrol station is 2.2 km from the main train station, easy to get on foot.
Your best option is to hitchhike with a thumb right under the sign before the ramp where the cars split by direction. There is a sharp bend and all cars slow down.
A lot of buses stop because of the restaurant and that makes option of asking people in front of the restaurant very unpleasant.
Since the above described way is both sided, hitchhiking from the same place will work too.
In all directions, long-distance
There are busy service stations for trucks just next to the Austrian-German border. Check on the page for Bregenz.