The nanoporous graphitic carbon materials (NGCM) have been prepared by a synchronous carbonization and graphitization process, using waste polyvinylidene fluoride (PVDF) as carbon precursor and Ni(NO3)(2)center dot 6H(2)O as the graphitic catalyst. It reveals that the carbonization temperature plays a crucial role in determining the pore structures as well as their electrochemical performances. Increasing the carbonization temperature from 800 to 1200 degrees C, the corresponding porosity has slightly decreased, accompanied by an increase of graphitization degree. Next, to further improve the electrochemical performance of the sample prepared at 800 degrees C, a novel redox additive of 4-(4-nitrophenylazo)-1-naphthol (NPN) with different amounts has been introduced in 2 mol L-1\ KOH electrolyte. Therein, the specific capacitance by adding 4 mmol L-1 of NPN can reach 2.98 times higher than the pristine value. Apparently, the mixed electrolytes have largely enhanced the electrochemical performance, which is expected to be applied in the field of high performance supercapacitors.