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In Klagenfurt themotorway takes you either east or west. If you are heading south there is another good option to hitchhike in the city, but there is no motorway.
If you are heading west the Park & Ride near lake Wörthersee might be your best option. Take bus number 10 from Heiligengeistplatz (next to the city center) to Minimundus P+R. It should take you about 10 minutes to get there by bus. Just hitchhike from the bus stop directly, there is a motorway onramp some 200m down the road. You might also find rides going east, it is however less likely than in the east of the city.
To get to this hitchhiking spot you can also take the S1 train from Klagenfurt main station in direction of Villach. Get off at Klagenfurt West, walk down to the four lane road (it is parallel to the tracks) and there is the bus stop.
If you want to go to Slovenia you should consider trying the option indicated below. There are not a lot of cars going to Slovenia via Villach.
Personal experience: But even as many cars were passing by, though no one stopped for us in about 2-3 hours (we went by train, then).
If you are heading east the roundabout next to IKEA and METRO might be a good option for you. Take bus number 50 from Heiligengeistplatz (next to the city center) to IKEA. The bus journey takes about 20 minutes. Next to the IKEA parking there is a big roundabout just before the A2 motorway onramp. Cars can stop there because there is one street just coming from a parking lot next by.
Heading south towards Ljubljana
Heading south for Slovenia and Ljubljana your best option in Klagenfurt is probably not the motorway. There is a lot of traffic from Slovenia going to Klagenfurt (and vice versa) via the Loibl/Ljubelj Pass. Take bus number 80 or 85 from Heiligengeistplatz (next to the city center) to Südring. Hitchhike from the bus stop, it is next to a traffic light. There is usually a lot of traffic to Slovenia.
Update January 2020: in this exact position, there's a bus stop with a bench in front of the ENI Gas Station. We (M+F/20s) had a sign "SLO" and waited for less than 3 minutes to get a ride in this direction. Should definitely try both people who's going in the direction, but also people fueling their cars as it's a typical stop before heading to Slovenia.