Schaan is the biggest city in Liechtenstein with around 5800 inhabitants.
There is a Youth Hostel in Schaan. You can also visit some mountains and relax in the countryside, but after one day you have explored the most. It is near the Rhine river and at the Swiss border. You can walk to the motorway A13 if you want.
For more information about hitching out of Schaan, have a look at Liechtenstein.