Currently used activated carbon electrodes from commercial products contain mostly micropores (<2 nm), which are not easily accessible to electrolyte ions. Therefore, mesoporous carbons, with their more accessible porous infrastructure, are promising materials to maximize the capacitance in electrochemical capacitors. This paper reports a new hybrid carbon nanofiber architecture having mesopores with a narrow distribution, highly accessible surface area, low resistivity, and high stability by electrospinning of starch without using the template method for the first time. By using the natural ability of the starch lamellar structure and controlling the carbonization temperature, we successfully fabricated a new hybrid carbon architecture consisting of CNT reinforced-carbon nanofibers with a pore diameter of 4.76 nm and pore volume of 0.31 cm³ g⁻¹. It shows a higher specific capacitance (170 F g⁻¹) and electrical conductivity (2.1 S cm⁻¹) than other carbon materials derived from synthetic polymers and free-standing CNT papers.