High molecular weight polyacrylonitrile (PAN) with low dispersity has been successfully synthesized utilizing reversible addition-fragmentation chain transfer (RAFT) polymerization. A comprehensive study was performed to understand the influence of reaction temperature, RAFT agent structure, and [M](0):[CTA](0)[/](0) on the polymerization kinetics, molecular weight, and dispersity. Enhanced control is attributed to reduction of side reactions by conducting the polymerization at lower temperature, and optimizing the radical exchange between active and dormant states via appropriate selection of RAFT agent and initiator. (C) 2015 Wiley Periodicals, Inc.