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Mitrovica is a city in Kosovo. It is divided into two parts by a river, with the North being predominantly Serbian and the South being predominantly Kosovar.
Walk along the main street towards the South until you reach the bridge crossing the M2. If you go under it, you can hitchhike in both directions. There is a tunnel, that direction is Pristina and you can likely get a direct ride. Towards Peja you can go in the opposite direction or on top of the bridge (not tried yet) and you will likely have to take several short rides.
As always in Kosovo, be wary of inofficial taxis and even (seemingly) official ones. They might tell you they'll take you for free - but that can always be a lie as a friend experienced.
Crossing to the North or South
Even though there are KFOR patrols on the river bridge dividing the city, you will not be checked. The North side uses Serbian Dinar as opposed to the Euro, but many places still take Euro. Be careful that they use an appropriate conversion rate.