Geolocation of high frequency (HF) transmitters at distances in the order of 2000 km is possible by exploiting the time difference of arrival (TDoA) among multiple distributed single antenna receivers. HF radio signals propagate via skywaves between the Earth‐Ionosphere medium and the signals are received through non‐line‐of‐sight mode. This experimental study demonstrates that it is possible to evaluate the TDoA between two receivers for a HF radio broadcast signal propagating through the ionospheric channel. The HF propagation path geometry for one hop propagation mode is explained. Simulations are performed using this model to evaluate the theoretical TDoA between the signals received at two synchronized receivers. In the second step, two remotely controllable receivers built to capture distinct HF signals are deployed in two cities in France. Radio broadcast signals from different HF transmitters across Europe are captured simultaneously on the two synchronized receivers. The TDoA is obtained by cross‐correlating the captured signals from the receivers. The TDoA obtained by experimental and simulation methods are compared for different radio propagation paths and results show some very good agreement.