The historic center, which is called San Marino Città, is a gorgeous medieval town and it's also part of UNESCO heritage. I definitely recommend a trip there, if you happen to be somewhere near.
When I went to school there, I regularly missed the bus so I had the chance of doing a few walks down to my home. It's a bit steep, since the town is located at the top of mount Titano at 700m of height, but it's truly charming.
When I tried to buy stamps direct from SM back in the 70s, and addressed mail to the SM post office, my local (USA) post office did not believe that there was a country with that name. He went thru their giant post office reference book and hey there it was !
I hike across Liechtenstein from time to time. A very light but picturesque set of trails for one day (30-50km). I usually start at the south border in a Switzerland town, cross the country up north and enter Austria.