The laser ablation of a photosensitive triazene polymer was investigated with a ns XeCl excimer laser over a broad range of thicknesses (10-400nm). We found that the ablation threshold fluence increased dramatically with decreasing film thickness for films thinner than 50nm. Ablation on substrates with different thermal properties (sapphire, fused silica, PMMA) was investigated as well, and a clear influence of the substrate material was obtained. A mathematical model combining thermal diffusion and absorption effects was used to explain the experimental data. The model is in good agreement with the experimental data and shows that heat diffusion into the substrate plays a crucial role for the ablation process of very thin film