Two ashless dithiocarbamate derivatives, octyl 2-(dibutylcarmothioylthio) acetate (DDCO) and S-dodecyl 2-(dibutylcarbamothioylthio) ethanthioate (DDCS), were prepared. Thermal stabilities tests were conducted with a thermo-gravimetric analyzer (TGA). The tribological properties of each compound and their combinations with ZDDP in a mineral oil (HVI WH150) were evaluated using a four-ball tester. X-ray absorption near-edge structure (XANES) spectroscopy was used to characterize the chemical properties of tribofilms generated from DDCO, DDCS and their combinations with ZDDP. According to the TGA results, the synthesized compounds possess good thermal stability (initial decomposition temperatures are above 270 degrees C). It can be found that all the prepared compounds have better friction-reducing capacity than ZDDP, with anti-wear performance and extreme pressure property worse than ZDDP. However, their combinations with ZDDP perform better than ZDDP in tribological properties. The results of the XANES analyses indicate that the composition of the tribofilms from DDCO or DDCS is organic sulphide on the outer surface and pyrite with a little sulphite in the inner layer, which also suggests the -SC(=S)-N- part in additives structure plays key role in tribol-chemical behaviour. The XANES spectra of the combinations exhibit interestingly that the addition of DDCO or DDCS can increase the length of polyphosphate chain in the tribofilms. (C) 2008 Elsevier Ltd. All rights reserved.