Carbon nanofibers (CNFs) have been synthesized from thermoplastic polyvinylpyrrolidone (PVP) using electrospinning in combination with a novel three-step heat treatment process, which successfully stabilizes the fibrous morphology before carbonization that was proven to be difficult for thermoplastic polymers other than polyacrylonitrile (PAN). These CNFs are both mesoporous and microporous with high surface areas without subsequent activation, and thus overcome the limitations of PAN based CNFs, and are processed in an environmentally friendly and more cost effective manner. The effects of heat treatment parameters and precursor concentration on the morphologies and porous properties of CNFs have been investigated, and their application as anodes for lithium ion batteries has also been demonstrated.