The results of photoelectric measurements in salts of planar complexes of mono- and dianionic metal dithiolenes with a variety of cations, such as 2, 2′ ‐ and 4,4′-bipyridinium derivatives, are described. It is shown that by specific combinations of ligands, metals, anionic charges and cations photoconductivity gain and spectral response to specific wavelength regions can be tailored. On the basis of ion pair charge-transfer (IPCT) mechanism a model is given according to which photoconductivity of metal dithiolene complexes may be attributed to the photoinduced “reverse” charge‐transfer between anionic and cationic sites resulting in conducting anionic stacks of mixed‐valence.