High mechanical performance carbon nanofibers are highly required for the carbon nanofiber-reinforced composites, and it is necessary to develop novel precursors for the preparation of carbon nanofibers. In this work, blends of poly(acrylonitrile-butyl acrylate mono-butyl itaconate) (co-PAN) and polyamic acid (PAA) were electrospun into aligned nanofibers and the nanofibers were converted to carbon nanofibers by thermal imidization, pre-oxidation and high-temperature carbonization. FT-IR spectroscopy was applied to monitor the chemical structures of the nanofibers before and after pre-oxidation. Tensile tests were used to characterize the mechanical properties of electrospun carbon nanofibers (ECNFs). The microstructures of ECNFs were investigated by high-resolution TEM and Raman spectroscopy. The results indicated that the ECNFs derived from blend of co-PAN/PAA with molar ratio of 6/4 and with carbonization temperature of 1400 A degrees C possessed the highest tensile strength of 1212 MPa, which could be attributed to the ordered graphitic structures in ECNFs.