F0 fluorescence and thermoluminescence (TL) were recorded simultaneously on various dark-adapted leaf samples. Above 40 °C, a sharp peak of TL coincided with the onset of the heat-induced F0 rise. It results from a back-transfer of an electron from the secondary QB- to the primary acceptor QA of photosystem 2, followed by a luminescence-emitting recombination with Tyr-D1. This demonstrates that the critical temperature at which the F0 starts rising also corresponds to a shift towards the left of the QA↔QB- equilibrium.