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Periodic structures of sub‐half‐micrometer size are produced on the surface of different polymers [poly(ethylene terephthalate)], polyimide‐type Kapton (DuPont), and polyimide‐type XU 293 (Ciba‐Geigy)] by Nd:YAG laser irradiation at 266 nm wavelength. The obtained relief is observed by scanning electron microscopy characterized by x‐ray photoelectron spectroscopy, and an atomic force microscopy. A phenomenological explanation for the ripple formation in terms of generating waveguide modes on the polymer surface is proposed.