Branching in poly(methyl methacrylate) (PMMA) is produced by incorporating a pre-prepared polymeric chain transfer agent (PCTA) into a single stage radical polymerisation. Samples of PCTA having a range of transfer functionalities and molar masses were synthesised by modifying a methacrylate-based copolymer. Control of branching in PMMA has been studied as a function of transfer functionality and molar mass in the PCT A and a function of MMA and initiator concentrations in the MMA polymerisation. The branched samples of PMMA have been characterised by size exclusion chromatography (SEC) with multi-detectors to determine Mark–Houwink and other parameters to assess levels of branching. Some PCTA samples have been prepared with a UV chromophore to facilitate characterisation by SEC-UV.