Residual organic solvents have a great impact on the physical and mental health of equipment operators in industry and agriculture. Laser waterless cleaning technology of residual organic solvents on the surface of polyurethane coatings has great application prospects and is a good way to tackle the pollution problem. In this paper, the evolutionary behavior of a laser waterless cleaning mechanism and substrate surface state is analyzed. The influence law of laser energy density and scanning speed on the residual solvent cleaning effect was investigated. The optimal laser cleaning parameters were obtained by comprehensive evaluation of the substrate surface cleaning effect and microscopic morphology. The peak of solvent characteristics before and after laser cleaning was detected by Raman spectroscopy. The results demonstrated that the laser cleaning effect was better with the increase of energy density or the decrease of scanning speed in the substrate damage range, and the best laser cleaning parameters were laser energy density of 0.24J/c m 2 and scanning speed of 500mm/s. A significant reduction of the peak of Raman spectroscopy was found, reflecting the excellent effect of laser waterless cleaning of residual organic solvents.