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One of the best solutions to get the border and in general Ljubljana etc is to take the train from main train station in Rijeka. You have to pay max. 3 euros ticket for Ilirska Bistrica (Slovenia) and after one hour long drive with train you have to walk from train station to the main spot. Ask local people there and they will show you how to come there. Its a 5-10 minutes minute walk from the train station. When you reach the spot you can easy get a ride to Postojna and then Ljubljana. Second solution: see the "Direction Trieste and Italy". But the first one is much more better and easier.