Anatase titanium dioxide (TiO2) nanocrystals with different percentages (up to 95%) of exposed {101} facet and different concentration ratios of bulk single-electron-trapped oxygen vacancies (SETOVs) to surface oxygen vacancies (SOVs) were prepared by alcohol-thermal method with nanotube titanic acid as the precursor in combination with solidstate reduction by NaBH4. The as-prepared TiO2 nanocrystals were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, electron spin resonance spectroscopy, and ultraviolet-visible light spectrometry. The effects of the percentage of crystal facets and the concentration ratio of bulk SETOVs/SOVs on the photocatalytic hydrogen production rate of TiO2 nanocrystals were investigated with positron annihilation lifetime spectroscopy as well as photocurrent test. Findings indicate that the percentage of the exposed {101} facets of the as-prepared TiO2 nanocrystals and their concentration ratios of bulk SETOVs/SOVs can be well tuned by properly adjusting the amount of NaBH4 and the reduction reaction time as well. Increasing percentage of the {101} facet of anatase TiO2 nanocrystals contributes to improving their photocatalytic hydrogen production activity, because the {101} facets of the anatase TiO2 nanocrystals possess enriched electrons and can act as the reduction sites to enhance the reduction reaction of H+ affording H-2 in the sacrifice system of splitting water. Both the bulk SETOVs and SOVs contribute to the improvement of the light absorption while SOVs can facilitate the separation of photogenerated charges, thereby adding to the photocatalytic activity. However, the bulk SETOVs and excessive SOVs are also the combination centers of photogenerated charges, which means it is essential to maintain a suitable concentration ratio of the bulk SETOVs/SOVs so as to enhance the light absorption and achieve the best separation efficiency of photogenerated charges and achieve the best photocatalytic activity for hydrogen production. Particularly, when anatase TiO2 nanocrystal with a high percentage (95%) of exposed {101} facet is reduced by NaBH4 at a mass ratio of 2: 1 for 20 min, the resultant reduced H-TiO2 nanocrystal (denoted as H-TiO2-R20(2:1)) provides the highest photocatalytic hydrogen productive rate. Furthermore, the combination of 0.5% Pt/H-TiO2-R20(2:1) with 0.5% Pt/WO3 can split water to simultaneously produce H-2 and O-2 , showing promising potential for splitting water affording hydrogen and oxygen. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.