New precursors, poly(acrylonitrile-co-crotonic acid) (poly(AN-CA)) and poly(acrylonitrile-co-itaconic acid-co-crotonic acid) (poly(AN-IA-CA)) copolymers, for the preparation of carbon fibers, were explored in this study. The effects of comonomers with acidic groups, such as crotonic acid (CA) and/or itaconic acid (IA), on the stabilization of nanofibrous polyacrylonitrile (PAN) copolymers were studied. The extent of stabilization, evaluated by Fourier transform infrared spectroscopy, revealed that the CA comonomer could retard/control the stabilization rate of PAN, in contrast to the IA comonomer, which accelerated the stabilization process. Moreover, the synthesized PAN copolymers containing CA possessed higher Mv than those of the IA copolymers and also showed outstanding dimension stability of nanofibers during the stabilization, which may be a useful property for improving the dimensional stability of polymer composites during manufacturing.