A new phenomenon of a reversible photoinduced coloration caused by light irradiation is discovered and investigated in superionicRbAg4I5crystals. The reversible photoinduced absorption is found to be a result of irradiation by light with wavelengths in the region from 420 nm to 450 nm. The proposed mechanism of the discovered effect is associated with ambipolar diffusion of screened by mobile ions optically excited electronic carriers. The processes of color centers creation in superionic crystalsRbAg4I5due to additive coloring in iodine vapours, ionic implantation and γ-ray irradiation are considered.