The chemical modification of polycrystalline CuInSe2 absorber surfaces by the so-called Cd partial electrolyte (PE) treatment was studied by synchrotron X-ray photoelectron spectroscopy (SXPS). The Cd PE treatment was found to remove surface indium oxides and hydroxides and segregated sodium compounds. A hydroxide-terminated CdSe surface layer of one monolayer thickness is formed by the partial electrolyte treatment. The reaction mechanism is discussed as substrate site-controlled exchange reaction, where surface indium is removed and replaced by cadmium. Electronically, the Cd PE treated surface is inverted and exhibits a surface barrier which is by 0.2 eV higher than a comparable structure that was prepared by the vacuum deposition of one monolayer of US onto clean CuInSe2. (c) 2004 Elsevier B.V. All rights reserved.