An experimental study was carried out for the development and characterization of innovative photopolymerizable siloxane-modified acrylic formulations for possible use as protective coatings of stone substrates. The kinetics of the radical photopolymerization mechanism induced by UV radiations in presence of a suitable photoinitiator was studied by a calorimetric analysis by varying the atmosphere (oxygen or nitrogen) and the composition of the mixtures, in particular of the UV photoinitiator.The reactivity, expressed in terms of both heat developed and rate of reaction, was generally found to decrease when the photopolymerization was carried out in air, due the inhibiting action of the oxygen towards the free radical polymerization. The addition of a proper thiol to the acrylic modified resin was found to reduce the adverse effect of oxygen on the kinetic reaction and on the degree of conversion. This result allowed to reduce the content of the photoinitiator and to increase the content of the siloxane in the acrylic based mixtures. The effect of the change of the composition of the formulations on the kinetic behaviour of the acrylic based resins was also analysed by calorimetric analysis. Calorimetric experimental data were fitted to a simple kinetic model for radical photopolymerization reactions. Finally, a proper relationship between the glass transition temperature and the total extent of reaction was applied to the experimental data. A good agreement between the experimental data and both the theoretical models was generally found.