The effects of heat and surface treatments used in the fabrication of CuInSe2 (CIS) single-crystal and thin-film solar cells are investigated, and the associated dominant defect states are identified using high-resolution photoluminescence (PL) and deep-level transient spectroscopy (DLTS) measurements. The results are correlated with junction electrical characteristics, and comparisons between thin films and single crystals are established. For the first time, direct evidence for several major defect types (Cu vacancies, Cu at In sites, and In at Cu sites) responsible for the majority-carrier type of the CIS is presented based upon spectroscopic atomic imaging of the n- and p-type semiconductor surfaces. Radiative recombination levels of extrinsic origin resulting from the surface processing (including polishing, etching, and annealing) were detected in the near surface region of the CIS single crystals, but not in the thin-film material having the same composition. The energy locations and depth of these states are responsible for the formation of an interfacial layer that is confirmed from frequency-dependent capacitance-voltage (C-V) data. The DLTS measurements on single-crystal and thin-film heterostructure {i.e., [Cd,Zn]S/CIS} devices (of nearly identical chemical compositions) have also confirmed the presence of a dominant trap level in the 270-meV region above the valance band. However, the trap density is some two orders of magnitude lower in the thin-film device, giving evidence that this processing-related defect level is responsible for the inferior performance of the single-crystal solar cells.