Laser ablation processing method for debris-free and efficient removal of materials comprises the step of using a refrigeration device to condense the water vapor and form a thin frost layer on the materials at temperatures below the freezing point. The residual debris produced during the ablation process deposits on the frost layer that covers the material, which is easily removed when the frost layer melts. At the same time, the frost layer in the laser irradiation area melts to a liquid layer, which can effectively reduce the deposition of debris on the inner wall of the groove and thus improve the efficiency and quality of laser ablation. The method is applicable to debris-free laser processing on an arbitrary curved surface.