The results of investigation of the electrophysical and photoelectric properties of complex copper chalcogenides are presented, namely, the properties of CuSnAsSe3, which exhibits ferroelectric properties, and CuInAsS3, which exhibits ionic conductivity. The spectral and temperature regions of photosensitivity of these crystals are determined. The depth of the level of carrier trapping centers, which manifest themselves under thermal activation, are evaluated from the analysis of thermally stimulated conductivity (TSC) curves in CuInAsS3. DOI: 10.1134/S1063776112100111