AbstractA novel cationic gemini surfactant has been readily synthesised in 70 % total yield. The functional gemini surfactant can act both as an emulsifier and an atom transfer radical polymerisation (ATRP) initiator in mini-emulsion polymerisation of methyl methacrylate (MMA), in which no other emulsifier was required. 1-(Dimethylamino)dodecane (N,N-dimethyldodecylamine, DMDA) was found to be a good ligand in the activator generated by electron transfer (AGET) ATRP reaction. Kinetic studies indicated that the polymerisation featured controlled/living radical polymerisation.