The main four-lane highway in Slovenia goes from the coast in Koper, through Ljubljana to Maribor, then up to the Austrian border. The secondary roads are more scenic, and still quite good.
For some scenic excitement check out the Loibl pass from Austria and the Vršič pass in the Triglav National Park.
Slovenia has a very short coastline, but Piran and Portorož on the seaside are very scenic. Koper is industrial.
Just a bit east of Ljubljana on the main highway is a village called Vransko that has a delightful little motorcycle museum: Motorcycle museum Vransko :: museum
A little further to the north-east of Ljubljana is a mountain valley called Logarska Dolina. My favorite ride.
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