By using an advanced polarization modulation infrared reflection adsorption spectroscopy (PM‐IRRAS) device it is possible to study the photopolymerization of an ultrathin layer of a porphyrin monomer in real time. The method can be compared with the indirect UV/Vis method previously introduced by our group. With PM‐IRRAS it is possible to analyze polymerization kinetics of photopolymerization at various temperatures to determine the activation energy of the reaction.