X-ray absorption near edge structure (XANES) spectroscopy was used to monitor the products formed during the breakdown of the engine additive ZDDP during its action as a protective tribochemical agent. This investigation examines the film formed under various physical conditions on a near hypereutectic Al-Si alloy. For the first time, tribochemical films (tribofilms) formed on a high silicon weight content alloy, with virtually no ferrous component have been studied. Phosphorus K-and L-edge spectroscopies show that under typical engine operating conditions, the tribofilms have similar chemical composition over a range of different test conditions. X-ray photoelectron emission microscopy (X-PEEM) reveals that the polyphosphate glasses formed vary in chain length within localized regions. The mechanical properties of the substrate and the tribofilms were acquired using a Triboscope Ò from Hysitron Inc. The elastic moduli can be extracted from the indentation curves and show that the tribofilms' mechanical properties are similar to those of the tribofilms which form on steel under similar conditions.