Polycrystalline Cu(In1−xGax)3Se5 thin films were prepared by four source evaporation with controlling and shielding of the molecular beams from elemental sources. Ga content x, can be controlled by deposition times of CuIn3Se5 and CuGa3Se5 layers, which form Cu(In1−xGax)3Se5 films through the interdiffusion. X‐ray diffraction analyses showed that the films with x≲0.5 have an ordered vacancy chalcopyrite and the films with x≳0.5 have a zinc blende structure. The optical band gap of the films linearly increased from 1.23 eV (x=0) to 1.85 eV (x=1) with increasing Ga content. The conductivity of the films was about 10−6/Ω cm and about 10−7/Ω cm under and above x=0.3, respectively.