The changes of defect characteristics induced by accelerated lifetime tests on the heterostructure n-ZnO/i-ZnO/CdS/Cu(In,Ga)(S,Se)₂/Mo relevant for photovoltaic energy conversion are investigated. We subject heterojunction and Schottky devices to extended damp-heat exposure at 85°C ambient temperature and 85% relative humidity for various time periods. In order to understand the origin of the pronounced changes of the devices, we apply current-voltage and capacitance-voltage measurements, admittance spectroscopy, and deep-level transient spectroscopy. The fill factor and open-circuit voltage of test devices are reduced after prolonged damp-heat treatment, leading to a reduced energy conversion efficiency. We observe the presence of defect states in the vicinity of the CdS/chalcopyrite interface. Their activation energy increases due to damp-heat exposure, indicating a reduced band bending at the Cu(In,Ga)(S,Se)₂ surface. The Fermi-level pinning at the buffer/chalcopyrite interface, maintaining a high band bending in as-grown cells, is lifted due to the damp-heat exposure. We also observe changes in the bulk defect spectra due to the damp-heat treatment.