Pulsed laser radiation at 193, 248, or 308 nm can etch films of polyimide (DuPont KaptonTM). The mechanism of this process has been examined by the chemical analysis of the condensible products, by laser-induced fluorescence analysis of the diatomic products, and by the measurement of the etch depth per pulse over a range of fluences of the laser pulse. The most important product as well as the only one condensible at room temperature is carbon. Laser-induced fluorescence analysis showed that C2 and CN were present in the ablation plume. At 248 nm, even well below the fluence threshold of 0.08 J/cm2 for significant ablation, these diatomic species are readily detected and are measured to leave the polymer surface with translational energy of ∼5 eV. These results, when combined with the photoacoustic studies of Dyer and Srinivasan [Appl. Phys. Lett. 48, 445 (1986)], show that a simple photochemical mechanism in which one photon or less (on average) is absorbed per monomer is inadequate. The ablation process must involve many photons per monomer unit to account for the production of predominantly small (<4 atoms) products and the ejection of these fragments at supersonic velocities.