Charleroi is a city in Wallonia, the southern part of Belgium
Brussels-South Charleroi airport is an important low-cost airlines hub located nearby the city.
You can hitchhike from the airport by standing at the car park exit gates located near the exit. It is good to ask the drivers where they are going when they are paying at the toll gates. Many cars are going in the direction of Brussels and Lille.
From the city to the motorways
If you are in the city of Charleroi and want to take the motorways to Brussels, Mons/Paris or Liège/Germany, the best way is to reach the Square Yernaux (the roundabout with the Marsupilami) and stand along the way in to the A54.