Copper (Cu)-catalyzed carbon nanofibers (CNFs) were used as an alternative of the conventional platinum-noble-metal-based catalyst at the counter electrode (CE) of a dye-sensitized solar cell (DSSC). The CNFs were grown on activated carbon microfiber powder (PACF) using chemical vapor deposition (CVD) and the Cu nanoparticles (NPs). The Cu NPs served simultaneous roles: (i) as the CVD catalyst for the growth of the CNFs; (ii) as an enhancer of the electrode conductivity; and (iii) as a catalyst for the reduction reaction. The Cu-CNF composite was applied as a thin layer on the fluorine-doped tin oxide glass using the simple doctor blade method. The prepared Cu-NP-dispersed PACF/CNF composite was characterized using various spectroscopic techniques, including scanning electron microscopy, Fourier transform infrared ray, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. The electrochemical tests showed that the Cu-PACF/CNFs had a high electrocatalytic activity and low charge transfer resistance (1.26cm(2)), using the cyclic voltammetry and electrochemical impedance spectroscopy measurements. The DSSC fabricated with Cu-PACFs/CNFs exhibited a power conversion efficiency value of 4.36%, open circuit voltage of 0.75V, short circuit current density of 11.12mAcm(-2), and fill factor of 54%. The prepared transition metal-CNF composite was simple to develop and can potentially be used as an efficient catalyst at the CE of DSSCs. Copyright (c) 2014 John Wiley & Sons, Ltd.