A novel hydroxyl-functionalised initiator for atom transfer radical polymerisation (ATRP) was synthesised by esterification reaction of a non-reducing sugar, meso-inositol. Due to steric hindrance, one of the six hydroxyl groups present in the sugar was not derivatised to the corresponding 2-bromoisobutyrate. The macroinitiator was used in ambient temperature ATRP of a hydrophobic monomer, methyl methacrylate (MMA) and a hydrophilic monomer, oligoethylene glycol methacrylate (OEGMA) using tri(ethylene glycol) monomethyl ether (TEGMME) as the polymerisation solvent and CuCl/CuCl2/PMDETA as the catalytic system. Under these conditions, polymerisation proceeded on to high conversion while maintaining low polydispersity giving well-defined five-arm star polymers. Hydrolysis under basic conditions was carried out to deduce the number of linear chains that were attached to the sugar.