Ecuador is great for hitchhiking, just be careful in some places. Many pick up trucks. Drivers might ask for money, but usually not to Westerners. It's not the safest country to hitchhike though.
Buses in Ecuador are quite cheap, and will usually stop anywhere. Though on some roads there are none. In that case hitchhiking can be a good alternative, and you will be picked up quickly as well.
Many Ecuadorians are happy to pick up foreigners, and will less often ask for money for the ride. You will often find the first car that passes stopping for you.