The band offset at the CBD-ZnS/Cu(In,Ga)Se-2 (CIGS) interface and solar cells performance were investigated by means of X-ray photoelectron spectroscopy (XPS). The valence band maximum and valence band offset at the chemical bath deposition (CBD)-ZnS/CIGS interface region was directly measured using a XPS spectral multiplot. We found that the conduction band offset (CBO) at the CBD-ZnS/CIGS (ordered vacancy compound, OVC) interface was smaller than that of the evaporated ZnS/CIGS (OVC) interface. However, the CBO for the CBD-ZnS/CIGS (OVC) interface was still quite large for fabrication of high efficiency devices, although, in fact, high efficiency CBD-ZnS/CIGS devices were fabricated with good run-to-run reproducibility. The bandgap dependence of cell performance for CBD-ZnS/CIGS devices (large CBO) showed a tendency similar to that of CBD-CdS/ClGS devices (small CBO). Therefore, the observed decrease in cell performance for high bandgap devices is not interpreted in terms of the CBO. These results suggest that the band offset is not the predominant factor in achieving high efficiency CBD-ZnS/CIGS thin film solar cells. This finding suggests that the recombination mechanism of those wide-gap alloys is a bulk recombination. (C) 2003 Elsevier Science B.V. All rights reserved.