Electrospun and carbonized 3D nanofiber mats coated with olivine structured lithium cobalt phosphate (LiCoPO4) were formed by a Pechini-assisted sol–gel process as cathode material for lithium ion batteries. 3D nonwoven nanofibers were soaked in aqueous solution containing lithium, cobalt salts and phosphates at 80°C for 2h. Then, the composites were dried and annealed at 730°C for 2 to 12h in nitrogen atmosphere. Crystalline deposits were uniformly distributed on the carbon nanofiber surface. The “loading” of the cathode material on the 3D carbon nanofiber composites reached 300wt%. The electrochemical measurements revealed the discharge specific capacity (measured at a discharge rate of 0.1C and room temperature) reaching a maximum value of 46mAhg−1 after annealing time t =5h.