The C1s and O 1s electrons in polymethyl methacrylate etched by different incident laser intensities are analysed by x-ray photoelectron spectroscopy. The results show that when the incident laser fluence increases gradually,the percentage of carbon atoms in C-C bonds decreases while the one in carbonyl group (C=O) and alkoxy group (C-O) increases, and the percentage of oxygen atoms in C=O bonds increases while the one in C-O bonds decreases. Based on the analysis of the chemical structure, the energy level transition, energy diversion, and dissociation of bonds are theoretically examined, which is consistent with the experimental results.