Optical and photovoltaic properties of films produced by laser deposition of CuIn3Se5 and the effect of the temperature conditions of film synthesis on these properties are studied. The composition of the films deposited onto substrates held at room temperature coincides with that of the target, with the films obtained in the vitreous state. Heating of substrates during deposition leads to a larger fraction of the crystalline phase and lower fraction of Se in a film. Annealing of glassy CuIn3Se5 films in a vacuum at temperatures of up to 700 K causes their crystallization without changes in composition. The photosensitivity of the films is highest at annealing temperatures of 510–600 K.