The driving-force dependence of bimolecular fluorescence quenching by electron transfer in solution, the Rehm–Weller experiment, is revisited. One of the three long-standing unsolved questions about the features of this experiment is carefully analysed here, that is, is there a diffusional plateau? New experimental quenching rates are compiled for a single electron donor, 2,5-bis(dimethylamino)-1,3-benzenedicarbonitrile, and eighteen electron acceptors in acetonitrile. The data are analysed in the framework of differential encounter theory by using an extended version of the Marcus theory to model the intrinsic electron-transfer step. Only by including the hydrodynamic effect and the solvent structure can the experimental findings be well modelled. The diffusional control region, the “plateau”, reveals the inherent distance dependence of the reaction, which is shown to be a general feature of electron transfer in solution.