The C 1s, F 1s, and O 1s electron spectra for polymethyl methacrylate (PMMA) and polytetrafluoroethylene (PTFE) irradiated by KrF excimer laser with 248 run wavelength were analyzed by the X-ray photoelectron spectroscopy (XPS) method. The results show that, after irradiation by the laser, the percentage of the carbon atoms of C-C bond decreases and the percentage of C=O bond increases for PMNM, while for PTFE percentages of both C-C bond and CF2 group decrease drastically, respectively. Moreover, it was found that C-O bond and other complex carbon-oxygen groups appeared for PTFE. The photon-chemical processes associated with the energy level transitions, energy diversion, and dissociation of bonds in the interaction were theoretically analyzed based on the chemical structures of PTFE and PMMA. Our analyses can successfully explain that PMMA can be effectively etched by KrF excimer laser with 248 nm wavelength can efficiently etch the PMMA, but the surface of PTFE can only be modified by it. (c) 2006 Elsevier B.V. All rights reserved.