The activators generated electron transfer (AGET) method coupled with atom transfer radical polymerization (ATRP) is shown to be a simple and well controlled approach for surface-initiated polymerization of 2-hydro-xyethyl methacrylate (HEMA) on regenerated cellulose (RC) membranes. The AGET-ATRP method has been optimized with respect to the initiator concentration, the polymerization reaction time and the reducing agent (activator) concentration. Control of polymer grafting on the external membrane surface versus the internal pore surface of RC ultrafiltration membranes was investigated using different pore filling solvents having a wide range of viscosity and reactivity during ATRP initiator immobilization via acylation of RC hydroxyl groups. The effectiveness of the pore filling solvent in limiting grafting inside the membrane pores was found to depend on both its viscosity and reactivity. Rejection of BSA and dextran was used to probe changes in pore size. Glycerol was found to be the most effective pore filling solvent, indicated by a significant degree of modification of the membrane surface with grafted polyHEMA but only a very minor increase in solute rejection.