Vorarlberg is on of the states of Austria. It lays on the right bank of Rhine river, at the east end of the Lake of Constanz. It borders Germany on the north, Switzerland and Lichtenstein on the west and Tirol state on the east, separated by Arlberg massif.
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The language locals speak belongs to the family of Allemanic languages. Everybody speaks high German (hochdeutsch) and vast majority of people English as well.
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.