Phosphorous and sulfur L- and K-edge X-ray absorption near edge structure (XANES) spectra were recorded to characterize the surface chemistry of the tribofilms derived from a commercial zinc dialkyldithiophosphate (ZDDP) and its blends with overbased calcium and magnesium salicylate detergents. The results show that the chemical structure of the tribofilms generated from the mixture of ZDDP and detergents is different from that of the tribofilm derived from ZDDP alone. However, the two kinds of detergents inhibit ZDDP from forming tribofilm, producing thinner polyphosphate films. Though XANES analysis does not provide definite evidence to the existence of magnesium element in the tribofilms, it is likely that calcium or magnesium has been incorporated therein. Moreover, ion exchange reaction and the formation of zinc polyphosphate film may occur simultaneously during sliding. However, calcium or magnesium (poly)phosphates do not contribute to reduce friction an of a steel-steel pair. (C) 2009 Elsevier Ltd. All rights reserved.