By the use of ultraviolet laser pulses of microsecond and millisecond duration it is shown that the chemistry of the transformations of Kapton by UV laser radiation is strongly dependent on the intensity (power/unit area) of the laser beam. With these long pulses, the polymer was not ablated. The decomposition resulted in 51% of the polymer weight being converted to gaseous products consisting mostly of CO (67%), HCN (15%), C2H2(12%), and some (<5%) CO2. The major solid product that remained was ‘‘glassy’’ carbon which was identified from its Raman spectrum. This material can be viewed as the product of the secondary addition reactions of the residue that is left after the loss of the gaseous products listed above. With 20 ms pulses, the evolution of the gaseous products increased linearly with intensity and the product composition was constant within the experimental uncertainty over a 12‐fold range of intensity up to 50 kW/cm2(≡1 kJ/cm2). These results show that pulses of duration much greater than ns do not lead to ablation even at fluences that are 104greater than the threshold for ablation using nanosecond pulses. It is therefore more appropriate to view the ablation of this polymer by UV laser pulses of nanosecond duration as being due to the scaling of an intensity threshold rather than a fluence threshold as has become the practice. ©1995 American Institute of Physics.