The photopolymerization of various mesogenic methacrylates (MEMs) by using an aluminium porphyrin complex (MTPP) as a photocatalyst has been investigated to show that the resulting polymers are ’living’ in nature. The polymerization of 6-[4-(4-cyanophenylazo)phenoxy]hexyl methacrylate (MAC) was exceptionally slow when compared to other mesogenic methacrylates, such as those containing ester and/or cyano groups in their mesogens. Interference of the light absorption of MTPP and/or the active propagating chain end by the MAC itself has been considered as being one possible reason for its slow polymerization, as a result of electron spectroscopy studies. Addition of methylaluminium bis(2,4-di-t-butylphenolate) greatly accelerated the polymerization of MEMs initiated with MTPP, as was also observed in the case of methyl methacrylate (MMA), with the exception of MAC, to yield polymers with very narrow molecular-weight distributions. Copolymerization of various MEMs with MMA revealed that both types of monomer are similar in their copolymerization reactivities. Poly(MEM)s formed with MTPP were found to have a higher content of syndiotactic triads than those obtained with a radical initiator. The phase transition behaviour of the polymers that were obtained was studied by focusing on polymers derived from 6{4[4-(methoxyphenoxy)carbonyl]phenoxy}hexyl methacrylate (MPM). This was because anionically obtained poly(MPM)s with higher contents of syndiotactic triads were reported to show different thermal behaviour from those poly(MPM)s formed via a radical mechanism. It appeared that poly(MPM)s obtained with MTPP have identical thermal properties to the latter but not to the former. The reason for such a discrepancy is not clear at the present time.