This paper presents results of a detailed X-ray photoelectron spectroscopy (XPS) characterization of complex changes at a polyimide surface resulting from Ar+ ion beam modification. The changes in chemical composition in the surface layer lead to formation of a layer that can act as an alignment layer for liquid crystals. The goal of this paper is to report on the result of a combination of spectral subtraction and multivariate analysis for analysis of XPS spectra. Principal component analysis (PCA), applied to curve-fitting results of difference spectra and multivariate curve resolution (MCR), applied to raw spectra, provided consistent results, and allowed for extraction of chemical anisotropy, defining factor in the ion beam (IB) alignment mechanism. This study demonstrated that more detailed chemical information about complex systems can be obtained through application of multivariate analysis to XPS spectra and curve-fits. Further, this approach can be effectively used in the characterization of various complex materials to link chemical structure to their properties. (C) 2010 Published by Elsevier B. V.