Electrospinning is a relatively simple method to produce submicron fibers from solutions of different polymers and polymer blends. In this study, PAN (polyacrylonitrile) fibers web was fabricated by electrospinning, and then was pre-oxidated. Effects of pre-oxidated heating rate on the structure and property of pre-oxidation web were discussed in this article. Thermal gravimetric (TG) curves were used to compare the thermal stability of PAN pre-oxidated samples under different pre-oxidated heating rates. TG curves showed that the integral procedural decomposition temperature was the highest when the pre-oxidated heating rate was 5 degrees C/minute, that is, the thermal stability of pre-oxidated nanofibrou web was the best under this condition. Moreover, results showed that with pre-oxidated heating rate increasing, the rate of mass loss gradually increased by moisture content analysis. Effect of the heating rate on central degree of the pre-oxidated web was not obvious by differential scanning calorimetry analysis, and the cyclization and dehydrogenation formed the final structure of the aromatic by infrared spectroscopy analysis. Especially, carbon nanofibers could be obtained from the pre-oxidated nanofibers at pre-oxidated heating rate 5 degrees C/minute with smooth surface and small fiber dispersion as well as solid and no empty fiber structure of the section.