In this study, three different acrylonitrile (AN)-based polymers, including polyacrylonitrile (PAN), poly(acrylonitrile-covinyl acetate) [P(AN-co-VAc)], and poly(acrylonitrile-co-itaconic acid) [P(AN-co-IA)], were used as precursors to synthesize activated carbon nanofibers (ACNFs). An electrospinning method was used to produce nanofibers. Oxidative stabilization, carbonization, and finally, activation through a specific heating regimen were applied to the electrospun fibers to produce ACNFs. Stabilization, carbonization, and activation were carried out at 230, 600, and 750 degrees C, respectively. Scanning electron microscopy, thermogravimetric analysis (TGA), and porosimetry were used to characterize the fibers in each step. According to the fiber diameter variation measurements, the pore extension procedure overcame the shrinkage of the fibers with copolymer precursors. However, the shrinkage process dominated the scene for the PAN homopolymer, and this led to an increase in the fiber diameter. The 328m(2)/g Brunauer-Emmett-Teller surface area for ACNFs with PAN precursor were augmented to 614 and 564m(2)/g for P(AN-co-VAc) and P(AN-co-IA), respectively. The TGA results show that the P(AN-co-IA)-based ACNFs exhibited a higher thermal durability in comparison to the fibers of PAN and P(AN-co-VAc). The application of these copolymers instead of AN homopolymer enhanced the thermal stability and increased the surface area of the ACNFs even in low-temperature carbonization and activation processes. (C) 2016 Wiley Periodicals, Inc.