A range of polymerisable photochromic naphthopyrans were prepared via the synthesis of an acrylate moiety on either the naphthalene ring (R) and/or the di-aryl (Ar) rings on the 3-position of the naphthopyran. The monomers obtained (NA) were copolymerised with methyl methacrylate (MMA) and methyl acrylate (MA) by the RAFT (reversible addition fragmentation chain transfer) process in order to control the structure of the polymeric chains and accurately control the number of photochromic molecules per chain. Films were prepared with the synthesized photochromic polymers and their photochromic properties were assessed. We found that the fading rate of the photochromic dye was slower in a matrix of PMMA (higher Tg) than in a matrix of PMA (lower T g). By producing block copolymers of PMMA-b-poly(MA-co-NA), the fading rate was increased, and the production of PS-b-poly(MA-co-NA) further enhanced the speed of switching, as phase separation occurred between the poly(MA-co-NA) block and the PS block. This study presents an example of tuning the photochromic properties of a dye via variation of the architecture of its polymeric support.