TiO2 semiconductor is one of the important photocatalysts for solar light conversion. The challenge is how to improve their efficiency. Creation of porous structures on/in the fibers could favor them a higher surface area as compared to the conventional solid counterparts, which thus could make the achievement for the desired high efficiency. In present work, we report the fabrication of porous TiO2 fibers with high purity via electrospinning of butyl titanate (TBOT) and polyvinylpyrrolidone (PVP) combined with the subsequent calcination in air. It is found that the TBOT content in the spinning solution plays a profound effect on the growth of the fibers, enabling the synthesis of porous TiO2 fibers with tunable structures and high purity. The photocatalytic activity for hydrogen evolution of the as-fabricated TiO2 nanostrcutres has been investigated, suggesting that porous TiO2 nanomaterials with a high purity and well-defined one-dimensional fiber shape could be an excellent candidate to be utilized as the photocatalyst for hydrogen evolution. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.