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Formation of polystyrene thin film by the synchrotron radiation chemical vapor‐deposition method was investigated using a styrene monomer. Polystyrene film was deposited at the irradiated area and vicinity along the irradiated area on a Si substrate. The deposition rate depended on the monomer gas pressure, substrate temperature, and x‐ray wavelength. Polystyrene film at the irradiated area was insoluble in benzene solvent, while that at the unirradiated area was easily dissolved. A patterned film deposition could be successfully performed under an irradiation of synchrotron radiation through a Ni mesh mask. The pattern profile was influenced by the gap length between the Si substrate and mask and a clear pattern was obtained after benzene treatment.