Living free-radical polymerization via reversible addition fragmentation chain transfer (RAFT) polymerization in presence of a chain transfer agent (CTA) was used to synthesize a new series of molecularly imprinted polymers (MIPs) for phenytoin as template in order to drug delivery carrier. MIPs were synthetized based on acrylamide (AAm) and ethylene glycol dimethacrylate (EGDMA) by precipitation polymerization method with different cross-linker content (<= 83%). To distinguish effect of RAFT polymerization on the morphological and binding characterization of MIPs, polymer synthesis was also performed via traditional radical polymerization (MIP-TRP) in absence of CTA. Morphological, structural and thermal properties of polymers were studied by SEM, FT-IR, XPS and TGA analyses. RAFT polymerization led to similar to 10% increasing in capacity of MIPs. Also, it was resulted in increasing of apparent total number of binding site (N-T) of MIPs from 18.32 mg g(-1) by TRP to 26.07 mg g(-1) by RAFT. In MIP with lower cross-linker content (50%), living polymerization showed increasing effect on the imprinting factor (IF) and relative selectivity coefficients for analogue drug. The IF of MIP-TRP increased from 1.1 to 1.8 by MIP synthesis in presence CTA (MIP-RAFT). Results showed that drug loading on MIPs extended phenytoin release from 12 h (unloaded drug) to 40-140 h and MIP-RAFT presented more delayed release profile than MIP-TRP. (C) 2018 Elsevier Ltd. All rights reserved.