Abstract Polystyrene (PS) film has great application potential in the electronics industry, optical instruments, and biomedical equipment, for its excellent optical, insulating, and mechanical properties. The composition conversion mechanism of the nanosecond laser cutting PS film process was studied by Raman and thermal analysis simulation. Raman tests verified that laser cutting would not create new solid by‐products and only had an influence on a few chemical bonds. Thermal cracking indicated that the released gas by‐product was mainly Benzene derivatives with benzene ring as the main body, which were harmful to human health. Thermogravimetric‐infrared combined analysis showed that the weight loss reached maximum rate at 405.73°C and remained basically unchanged after 444.85°C. Moreover, a quality evaluation standard composed of cutting kerf zone and heat‐affected zone for nanosecond laser cutting of PS film was established. A three‐factor and five‐level orthogonal experiment was performed for research the cutting processes, and 2 (190 kHz)–4 (0.4 m/s)–4 (65) was the preferable process parameter combination by analysis comprehensively. Interaction analysis was also conducted to clarify the correlation between laser cutting factors. This work has an important guiding role in the industrial application of PS film laser cutting.
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