Hollow activated carbon nanofibers (H-ACNF) were prepared by concentric electrospinning of poly(methyl methacrylate) (PMMA) as a pyrolytic core precursor and polyacrylonitrile (PAN) as a carbon shell precursor, followed by stabilization, carbonization, and activation. The H-ACNF with 190 and 270 nm for core and shell diameter showed excellent mesoporous structure, and 1-D conducting pathway in employing as catalysts of counter electrodes (CEs) for dye-sensitized solar cells (DSCs). The mesaporous structure of H-ACNF represented surface area of 1037.5 m(2) g(-1) with average mesopore diameter of 17.4 nm. The overall conversion efficiency of H-ACNF is comparable to that of Pt CE because its characteristics promotes the electron and ion transfer, decreases the resistance of charge transfer, and increases the contact area between liquid electrolyte and H-ACNF. (C) 2013 Elsevier Ltd. All rights reserved.