Homogenous strontium titanate (SrTiO3) nanofibers were prepared via the electrospinning of precursor solutions containing both strontium and titanium salts. Photocatalytic activities of these SrTiO3 nanofibers for hydrogen generation from water were examined and compared to that of SrTiO3 nanoparticles. The nanofibers calcined at 700 °C showed the highest photocatalytic activity of 167 μmol/h/g among the SrTiO3 samples tested. The high activity was attributed to the ideal stoichiometric ratio of Ti/Sr, small crystallite size, high crystallinity, mesoporous structure, large surface area, and appropriate energy gap. These were confirmed through field emission scanning electron microscopic with energy dispersive spectroscopic observations, x-ray diffraction patterns, N2 gas absorption–desorption isotherm measurements, photoelectron yield spectroscopy in air, and UV-visible spectrophotometry.