Cationic photopolymerization is a convenient in situ polymerization method for organic thin film preparation. In this work, the polymerization mechanisms is applied for highly viscous cross-linking monomers, using tetra-alkylepoxyporphyrin (TAEP) as a case study. By comparing the UV-Vis spectra of the polymerized sample before and after the unreacted monomers have been dissolved, it is possible to estimate the polymerization yield. Am IR spectrum of a reference thick film confirms full polymerization. Scanning fluorescence lifetime microscopy and AFM show the uniformity of the polymer. It was shown that photopolymerization is highly dependent on the substrate nature and requires at best case a 10 min illumination at 90 degrees C. Thermal polymerization of the same sample requires 10 min heating at 150 degrees C in dark. It was also shown that TAEP works as a self-sensitizer for cationic photopolymerization. The proposed method is a mild and versatile technique for in situ preparation of thin polymeric films directly from chromophore monomers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6095-6103, 2009