Vinyl methacrylate (VMA) was homopolymerised and copolymerised with methyl methacrylate (MMA) by group transfer polymerisation at room temperature through the methacrylolic group, resulting in linear, soluble and reactive polymethacrylates with pendant vinyl ester groups. The reactivity ratios were found to be r(VMA) = 105 and r(MMA) = 0.0098 by the Tidwell and Mortimer method.