Surface-roughened TiO2 nanowires (NWs) were fabricated using co-electrospinning with different molecular weights of polyvinylpyrrofidone (PVP) polymer: low molecular weight PVP (M-w=360,000 g/mol) for the core region and high molecular weight PVP (M-w=1,300,000 g/mol) for the shell region. Together with the formation mechanism, their surface property, morphology, crystal structure, and photovoltaic performance were studied. The results showed that the surface-roughened TiO2 NWs had an enhanced specific surface area because of the rough NW surface compared to the pure TiO2 NWs. As a result, the short-circuit current density (8.94 mA/cm(2)) of DSSCs fabricated with the surface-roughened TiO2 NWs is higher than that (5.88 mA/cm(2)) of the pure TiO2 NWs. Therefore, the photoconversion efficiency of the surface-roughened TiO2 NWs exhibited a high value of 3.63% compared to that of the pure TiO2 NWs. This phenomenon can be explained by the enhancement of short-circuit current density by an increased dye adsorption; this is because of the increased specific surface area induced by the NW shrinkage due to the different thermal decomposition behavior of PVP depending on the different molecular weights of PVP. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.