Carbon nanofibers decorated with various metal oxide nanoparticles were fabricated by combining an electrospinning technique of bicomponent polymer mixture and a sol-gel reaction and subsequent carbonization process. Electrospun polymer nanofibers consisting of polyacrylonitrile (PAN) and poly(vinyl pyrrolidone) (PVP) with controllable diameters were fabricated with PAN/PVP core/shell types via phase-separation due to the immiscibility between two polymers. The electrospun nanofibers served as supporting materials with binding sites of PVP to incorporate titanium oxide precursor. Subsequently, the carbonization of the fibers led to the formation of carbon nanofibers@TiO2 for energy application, in which rutile TiO2 nanoparticles were decorated on the surface of carbon nanofiber. Especially, this TiO2 decorated carbon nanofiber electrode exhibited excellent electrochemical property in lithium-ion batteries (≈600 mA h g−1 at C/5 rate for 100 cycles). Furthermore, the carbon nanofibers were also successfully modified with other metal oxides, including NiO, SnO2 , and ZrO2 nanoparticles, in a similar manner.