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Results are presented on the ablation by 157 nm laser radiation of polytetrafluoroethylene (PTFE), polyimide, polyhydroxybutyrate (PHB), poly(methyl methacrylate) (PMMA), and poly(2‐hydroxyethyl methacrylate) with 1% of ethylene glycol dimethacrylate as a crosslinking monomer. Direct photoetching of PHB and undoped PTFE is demonstrated for laser fluences ranging from 0.05 to 0.8 J/cm2. The dependence of the ablation process on the polymer structure is analyzed, and insight into the ablation mechanism is gained from an analysis of the data using Beer–Lambert’s law and the kinetic model of the moving interface. Consideration of the absorbed energy density required to initiate significant ablation suggests that the photoetching mechanism is similar for all the polymers studied. © 1995 American Institute of Physics.