Grazing incidence X-ray diffraction (GIXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX) are combined to investigate the microstructure and chemical composition of the surface layer in Cu(ln, Ga)Se-2 (CIGS) thin films deposited using a three-stage co-evaporation process. According to the GIXRD and micro-region electron diffraction analyses, ordered defect chalcopyrite (ODC) structure does not exist in the surface layer and the surface and the bulk region of the CIGS film have the similar crystal structure. However, the results from the EDX data show that the compositional ratios of the Cu/(In + Ga) (Cu/III) have a gradient distribution across the whole surface layer. The surface layer shows a Cu-poor compositional characteristics and the Cu content increases gradually from the surface to the bulk of the material. The compositional depth profiles determined by XPS agree very well with the results of the EDX measurements. The thickness of the surface layer has been determined to be about 50-100 nm in consistence with that estimated from the compositional ratio of Cu/III. High density dislocations have been observed in the surface region of these samples by high resolution TEM analyses. Our results suggest that different compositions would induce different point defects in the surface layer. (C) 2011 Elsevier B.V. All rights reserved.