The human life faces serious energy shortage and environmental pollution problems, therefore developing a facile and environmental friendly strategy for synthesizing nanoparticles (NPs) with improved photocatalytic activity could pave the way for different applications. In the present study, one-pot/in-situ fluorine-free synthesis process has been examined toward the solvothermal production of anatase TiO2 nanoparticles with exposed facet orientation. This is an aim to achieve the excellent photocatalytic/photoelectrocatalytic performance. Most importantly addressing the global energy shortage, the synthesized TiO2 NPs represent superior performance in photoelectrocatalytic water splitting toward hydrogen production. The overpotential required to drive the hydrogen evolution reaction was -391, -346 and -283 mV vs. Ag/AgCl for P25, cubic and truncated octahedral NPs, respectively. Additionally, TiO2 NPs with exposed facets represent excellent photocatalytic performance toward environmental purification. As synthesized nanoparticles was examined via photocatalytic degradation of Acid Blue 5 and photo catalytic removal of NO gas. The enhanced photocatalytic and photoelectrocatalytic performance are associated to the effect of exposed facet orientation of final nanoparticles. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.