Herein, the composite carbon material of porous carbon nanofiber and carbon nanotube is developed via electro-blown spinning and one-step simultaneous carbonization and chemical vapor deposition without injecting every kind of reaction gas in proportion and removing catalyst in secondary processing. The carbon nanotubes are uniformly growing on carbon skeleton which dramatically improve the performances such as specific surface area (from 334.066 to 644.589m(2)g(-1)) and electrical conductivity (from 42.22 to 146.20Scm(-1)) comparing with porous carbon nanofibers. The different spinning parameters are investigated to optimize parameters, and the porous carbon nanofiber and carbon nanotube are studied and used as electrode for supercapacitors. The results showed that it possesses excellent electrochemical properties, including high specific discharge capacity (216.5Fg(-1) at 1.0Ag(-1)) and good cycle performance (retains similar to 98.68% after 5000 cycles). Moreover, the convenient one-step prepared method special throughout pores structure and superior performance provide a novel approach for designing new types of carbon composite materials which also possess potential application prospect in fields of catalyst, adsorption, etc.