The ionic products from excimer laser photoablation (λ=308 nm) of polyimide (Kapton) film have been studied as a function of fluence. Large ion masses up to about 900a.m.u. are easily observed, the mass distribution depending strongly on the fluence. Velocities of the emitted particles lie between 1400 and 10 000 ms-1, again dependent on the fluence. A mechanism to explain the high velocities is suggested consisting of ionisation of the surface polymer molecules followed by a Coulomb explosion combined with expansion of the high density gas formed by the photoablation.