Well-defined copolymer of acrylonitrile (AN) and maleic anhydride (MAn) has been successfully synthesized via reversible addition-fragmentation chain transfer polymerization. The polymerization kinetics and living/controlled features were thoroughly studied and confirmed. The thermal properties and spinnability of the prepared copolymers were investigated via differential scanning calorimetry, thermogravimetric analyzer, and electrospinning subsequently. When PAN-co-PMAn was used as precursors, nonwoven with crosslinked structures was obtained during electrospinning. (c) 2013 Wiley Periodicals, Inc.