Device-grade thin-film CuInSe2 was subjected to various chemical treatments commonly used in photovoltaic device fabrication to determine the resulting microscopic surface composition/morphology and the effect on II-VI/CuInSe2 heterojunction formation. HCI (38%), Br-MeOH (<1% Br), (NH4)2S, and NH4OH/thiourea solutions were used separately to modify the surface chemistry of the CuInSe2 polycrystalline films. Scanning electron microscopy was used to evaluate the resultant surface morphology. Angle-resolved high-resolution photoemission measurements on the valence band electronic structure and Cu 2p, In 3d, Ga 2p and Se 3d core lines were used to evaluate the chemistry of the chemically treated surfaces. CdS overlayers were then deposited in steps on these chemically treated surfaces. Photoemission measurements were acquired after each growth to determine the resultant heterojunction valence-band discontinuity between the CdS and the chemically modified CuInSe2 surface.