The equation of thermionic emission has been derived, which takes into account the presence of thin films of adsorbed gas-environment molecules on a cathode under conditions of high-voltage gas discharge. It is shown that the consideration of electron polaron tunneling mechanism leads to a significant (by more than an order of magnitude) decrease in the emission-current density. A comparison with the classical Richardson–Schottky equation is performed. The role of the polaron effect is shown to strongly increase with an increase in the applied electric field strength and a decrease in temperature, which is due to an increase in the electron work function because of polaron nature.