Photochemical electron transfer between freely diffusing molecules has been studied extensively. Here, we try to elucidate how much these works have contributed to the understanding of electron transfer. To this end, we have revisited the work performed in the experimental and theoretical areas of concern from the beginning of the 20th century up to the present day. We present a critical look at the major contributions and compile the current picture of a variety of phenomena around electron transfer in solution. This is based on two main developments, besides the theory of Marcus: encounter theories of diffusion and laser techniques in time-resolved spectroscopy.