We report on the preparation and characterization of Ag/LiCoO2 nanofibers (NFs) via the sol-gel electrospinning (ES) technique. Ag nanoparticles (NPs) were produced in an aqueous polyvinyl pyrrolidone (PVP) solution by using AgNO3 precursor. A viscous lithium acetate/cobalt acetate/polyvinylalcohol/water (LiAc/(CoAc)(2)/PVA/water) solution was prepared separately. A Ag NPs/PVP/water solution was prepared and added to this viscous solution and magnetically stirred to obtain the final homogeneous electrospinning solution. After establishing the proper electrospinning conditions, as-spun precursor Ag/LiAc/Co(Ac)(2)/PVA/PVP NFs were formed and calcined in air at a temperature of 600 degrees C for 3 h to form well-crystallized porous Ag/LiCoO2 NFs. Various analytical characterization techniques such as UV-vis, SEM, TEM, TGA, XRD, and XPS were performed to analyze Ag NPs, as-spun and calcined NFs. It was established that Ag NPs in the precursor Ag/LiAc/Co(Ac)(2)/PVA/PVP NFs are highly self-aligned as a result of the behavior of Ag in the electric field of the electrospinning setup and the interaction of Ag ions with Li and Co ions in the NE Ag/LiCoO2 NFs exhibit a nanoporous structure compared with undoped LiCoO2 NFs because the atomic radius of Ag is larger than the radius of Co and Li ion; thus, no substitution between Ag and Li or Ag and Co atoms occurs, and Ag NPs are located at the interlayer of LiCoO2 while some are left in the fiber. (C) 2013 Elsevier Ltd. All rights reserved.