Surface relief gratings (SRG) and self-organized nano-structures induced by laser light at 157 nut on the fluoropolymer poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA), films were obtained under well-controlled light exposure conditions. Regular and semi-regular spaced self-organized grating-like structures were created on polymeric films for similar to 7.5-100 mJ/cm(2) laser energy fluence. For lower laser fluence, the surface morphology of light exposed/non-exposed areas exhibited irregular-like structure morphologies, while polymer surface irradiation with energy fluence higher than 150 mJ/cm(2) causes progressively fading out of the regular patterns. Under the specific experimental conditions, the SRG and self-organization patterning have their origin in the development of a surface thermal instability (Rayleigh's instability), which is resolved itself into regular patterns on the surface of the fluoropolymer film. The thermal instability is due to the explosive polymer surface photo-dissociation at 157 nm and the build up of longitudinal and periodic surface stress, which eventually create the SRG and the self-assembled structures on the polymer. (c) 2007 Elsevier B.V. All rights reserved.