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Your best option is to get to a Area Servizio rest stop petrol station on the motorway. The easiest way to do that is to take bus line 51 G51 from Trieste bus station (around 2 3 Euro), . Bus G51 leaves once every half hour and get stops inside the bus station building instead of outside with the other busses. Get out some 30 minutes later at after the village of Sistiana in front of the big supermarket "Cooperative SocialiConad superstore" ex Bar in Duino Bianco. Keep walking on in the same direction the bus is going for about 400 meters, when you will 'll see a sign saying "Idea hotel" and a large fenced in slab of asphalt. Follow the path right here until you reach an Agip a small metal gate leading to a gas station on the statal road. The back of this gas station is connected with the rest area on the highway, direction Slovenia. To go direction Venice, just use the underground tunnel connecting the two rest areas. This spot seems to be most active during the morning and early afternoon, but even then there doesn't seem to be too much traffic, and most people were going to Monfalcone 15 minutes up the road. People seemed pretty friendly here, and we managed to get a ride in about 30 minutes. We also tried this spot the previous evening and it was completely desolate apart from a few police cars stopping to get dinner at the "Fast Eat Italy".