Cationic photocurable systems show important advantages with respect to the use of the radical process. The use of bio-renewable monomers will make the cationic process greener. We have reported the synthesis of a series of vinyl ether ester oligomers using enzyme catalysis under solvent-free conditions. We have reported the synthesis of epoxy functionalized bio-renewable monomers as well, that can be applied in cationic photopolymerization. The cationic UV-curing process was efficient in obtaining crosslinked coatings with a wide range of thermo-mechanical properties. The final properties were analyzed based on the monomer chemical structure. Glass or carbon fibers epoxy composites was achieved for the very first time. We have demonstrated that the crosslinking reaction proceeds via a radical-induced cationic frontal polymerization (RICFP), where the UV-surface activation of cationic ring-opening polymerization is able to promote the heat front that will activate a thermal initiator in the deeper layers. Because of the very high velocity of the reaction, we could obtain quickly epoxy composites maintaining the good thermo-mechanical properties. By this way, thicker cationic photocured materials can be achieved.