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Nova Gorica is a city in Slovenia. It is situated in the west of the country, bordering directly with Italy. It is kind of merged with the Italian city Gorizia. Nova Gorica has a small university, and quite a few casinos to get rid of all your money. Close to the city is the river Soča, which is a perfect spot for hot summer days. There are many beautiful places to see in the area.
There is a great spot in front of the Qlandia mall (exact spot can be found on this link: http://www.qlandia.si/it/il-centro-qlandia. To get there from Italy, there is a bus that leaves right in front of Gorizia train station (cost is 1 euro, payable on the bus. The bus does not run on Italian and Slovenian bank holidays). At one point, once you enter Slovenia, there will be a sign indicating the Center on the right: when you see it, go down at that stop. Walk forward for about 5 minutes (it is not the safest option but there is a path in the park nearby) till you see a roundabout. Walk straight and you will be in front of Qlandia mall. HHsardo, in April 2015, saw two local hitch-hikers getting a lift to a nearby village within 5 minutes. He himself then tried hitching to Ljubljana with a "LJ" sign and got a lift within 10 minutes to another spot by the highway.
To get to the spot from the main bus station information can be found on this link http://erasmusu.com/en/erasmus-nova-gorica/what-to-do/qlandia-3892.
Highway H4, directions Ljubljana or Palmanova
Take the free bus to Vrtojba. Step out as near to the H4 as possible. There are nice spots on both sides of the border going both directions.
From the city, direction: Ljubljana
A bus stop called "Kromberk Hrast" on the "Kromberška cesta" street, is located right after a crossroad with a streetlight. Some drivers prefer to take this way to get to the highway H4.
Bus stop "Grčna", across the street from supermarket "QLandia". Some drivers take this way to the highway. Some people might talk to you and suggest the spot described above. I can't really tell which is better. From this spot it is also possible to go towards Koper and Italy.
Direction: Kanal, Tolmin, Bovec
The best option is hitchhiking in Solkan. You can get there using free public transport - going until the last stop (parking place in Solkan where the bus turns). Pass the bridge (road to Brda), after there is a traffic light and a nice hh spot right after it!
Direction: Trieste, Monfalcone
Take the city bus to Šempeter, get off on the main square, near the church. Walk back the way bus came from, to the crossroad with streetlight, and turn left, walk past "Eurospin" supermarket, there will be a bus stop on the right side.