In this contribution, we would like to present structural and electrochemical characterization of composite carbon/TiO₂ fibers prepared by centrifugal force spinning. Monoclinic TiO₂-B is a very promising material with respect to lithium-ion insertion and unlike other TiO₂ allotropes, TiO₂-B crystallizes in monoclinic lattice with opened layered structure giving it extraordinary possibilities for lithium ion storage. Carbon fibers filled with TiO₂ particles were prepared using PAN as carbon source together with the mixture of sodium trititanate Na₂Ti₃O₇ and sodium hexatitanate Na₂Ti₆O₁₃ as TiO₂ source. The solution for preparation of fibers was made by dissolving PAN in DMF with dispersed hydrothermally synthesized Na₂Ti₃O₇/Na₂Ti₆O₁₃ nanorods. Fiberio Cyclone 1000M/D was used to spin the as prepared solution in the form of composite polymer/ceramic fibers which were heat treated in nitrogen atmosphere at 800°C subsequently. XRD measurements revealed that the sodium titanates were successfully transformed in the form of TiO₂ with either monoclinic or tetragonal lattice. Electrochemical measurements were performed in aprotic electrolyte against metallic lithium in a three electrode setup. Cyclic voltammetry shows response typical for mixture of two crystallographic phases of TiO₂ where TiO2-B is present.