Distinguishing the scattering contributions of isoelectronic atomic species by means of conventional x-ray- and/or electron diffraction techniques is a difficult task. Such a problem occurs when determining the crystal structure of compounds containing different types of atoms with equal number of electrons. We propose a new structural model of Cu(InxGa1-x)3Se5 which is valid for the entire compositional range of the CuIn3Se5–CuGa3Se5 solid solution. Our model is based on neutron and anomalous x-ray diffraction experiments. These complementary techniques allow the separation of scattering contributions of the isoelectronic species Cu+ and Ga3+, contributing nearly identically in monoenergetic x-ray diffraction experiments. We have found that CuIII3Se5 (III=In,Ga) in its room temperature near-equilibrium modification exhibits a modified stannite structure (space group I42m). Different occupation factors of the species involved, Cu+, In3+, Ga3+, and vacancies have been found at three different cationic positions of the structure (Wyckoff sites 2a, 2b, and 4d) depending on the composition of the compound. Significantly, Cu+ does not occupy the 2b site for the In-free compound, but does for the In-containing case. Structural parameters, including lattice - - constants, tetragonal distortions, and occupation factors are given for samples covering the entire range of the CuIn3Se5–CuGa3Se5 solid solution. At the light of the result, the denotation of Cu-poor 1:3:5 compounds as chalcopyrite-related materials is only valid in reference to their composition.