At first, the mixed solution of both polyacrylonitrile (PAN) in N,N-dimethylformamide (DMF) and multi-walled carbon nanotube (MWCNT) was electrospun so as to make PAN-based nanocomposite fiber web. The electrospun PAN-based carbon nanofiber web was prepared by stabilizing at 280℃, and by activating at 800℃ in steam atmosphere. Finally, the polypyrrole/MWCNT-carbon nanofiber composite web was prepared by polymerizing pyrrole to use Fecl3ㆍ6H2O as an oxidant on the carbon-MWCNT nanofiber. The electrodes of (1) bared carbon (2) MWCNT-carbon (3) PPy/carbon (4) PPy/CNT-carbon were prepared for a supercapacitor. Out of the electrodes, the electrochemical performance of 20 wt% polypyrrole/carbon-MWCNT composite nanofiber web electrode was the best as a value of 333F/g. This is because of the synergic effect of non-faradaic and faradaic mechanism.