A single-pot atom-transfer radical polymerization (ATRP) under microwave irradiation was first used to successfully synthesize polyacrylonitrile. This was achieved by using FeCl2/succinic acid as the catalyst and 2-chloropropionitrile as the initiator. Using the same experimental conditions, the apparent rate constant under microwave irradiation was found to be higher than that under conventional heating. The FeCl2/succinic acid ratio of 1:2 not only gives the best control of molecular weight and its distribution but also provides rather rapid reaction rate. When FeCl2 was replaced with CuCl, ATRP of AN does not show an obvious living characteristics. To demonstrate the active nature of the polymer chain end, the polymers were used as macroinitiators to proceed the chain-extension polymerization. (c) 2006 Wiley Periodicals, Inc.