In this work, the effect of carbon nanofibers (CNFs) addition on physicochemical characteristics of CNFs-reinforced epoxy matrix nanocomposites was studied. Poly(amide imide) solutions in dimethylformamide were electrospun into webs consisting of 250±50 nm fibers which were used to produce CNFs through stabilization and carbonization processes. As a result, the CNFs with average diameter of 200 ±20 nm were obtained after carbonization process. The nanocomposites with CNFs showed an improvement of thermal stability parameters and fracture toughness factors, compared to those of the specimen without CNFs, which could be probably attributed to the higher specific surface area and larger aspect ratio of CNFs, resulting in improving the mechanical interlocking in the nanocomposites. Also, the applied external loading can effectively transfer to CNFs because strong interactions are resulted between the epoxy matrix and the CNFs.