CuInSe2 thin films have been prepared by high Se vapor selenization of co-sputtered Cu–In alloy precursors within a partially closed graphite container. Cu–In alloys with different compositions were investigated. X-ray diffraction (XRD) analysis of the films showed mainly CuIn2 and Cu11In9 phases and the Cu11In9 peak intensity was found to increase as the alloy composition tended towards Cu-rich. A linear dependence of the alloy composition on the Cu/In deposition power was observed from energy dispersive analysis by X-rays (EDX). A three-fold volume expansion was exhibited by all the CuInSe2 films after selenization at 500–550 °C. Scanning electron microscopy (SEM) analysis of the films showed large and densely packed crystal structures with sizes above 5 μm. The CuInSe2 films exhibited single phase chalcopyrite structure with preferential orientation in the (1 1 2) direction. The EDX composition analyses of the films showed Cu/In ratio ranging from 0.43 to 1.2, and Se/(Cu+In) ratios from 0.92 to 1.47. The measured film resistivities varied from 10−1 to 105 Ωcm. The Cu–In alloy precursors with Cu/In ratio less than 0.70 were found to form CuIn3Se5 a defect chalcopyrite compound. All films were Se rich, with the exception of samples with very high Cu content.