The electrical properties of n and p‐type bulk samples of CuIn3Se5 have been studied in the temperature range from 80 to 300 K. From the analysis of the temperature dependence of electron and hole concentrations in the activation regime above 110 K, the activation energy and the density of states effective mass of the charge carriers are estimated to be 36 meV and 0.13me for n‐type samples, and 28 meV and 1.07me for p‐type samples, respectively. The relatively low value of the carrier concentration in n‐CuIn3Se5 and the value in p‐CuIn3Se5 being of the same magnitude as in CuInSe2 confirms that this compound is formed due to the presence of ordered arrays of electrically inactive donor–acceptor defect pairs (2 VCu1— + InCu2+). Below 110 K, the electrical conduction in the impurity band is due to nearest neighbor hopping mechanism. The relatively low magnitude of the electron mobility and its temperature dependence in the activation regime is explained by considering, in addition to the well‐established scattering processes, a mechanism that involves the scattering of the charge carriers by ordered arrays of donor–acceptor defect pairs. At lower temperatures, the variation of the mobility is explained by taking into account the theoretical model for the thermally activated nearest neighbor hopping of the charge carriers between localized states in the impurity band.