•CdS-loaded TiO2 microsphere with highly exposed (001) facet is synthesized.•CdS/TiO2 microsphere exhibits excellent photocatalytic H2-production efficiency.•(001) faceted surface is beneficial for the interfacial transfer of electron.CdS-loaded TiO2 microspheres with highly exposed (001) facets were prepared by hydrothermal treatment of a TiF4–HCl–H2O mixed solution followed by a chemical bath deposition of CdS onto TiO2 microspheres. The crystal structure, surficial micro-structure and photo-absorption property of the samples were characterized by XRD, FE-SEM, TEM and UV–vis diffuse reflectance spectroscopy, etc. The as-prepared samples exhibited superior visible-light-driven photocatalytic H2-production activity from lactic acid aqueous solution in comparison with CdS-sensitized TiO2 nanoparticles, whose surface was dominated by (101) facets. Photoelectrochemical measurement confirmed that (001) facet is beneficial for the transfer of photo-generated electron from CdS to TiO2 microsphere, which led to the unexpected high photocatalytic activity of CdS-loaded TiO2 microspheres.

•Anatase TiO2 micro-crystals with high-energy facet are synthesized by a simple one-pot hydrothermal method.•The percentage of exposed (001) facet is tuned by controlling the concentration of F− ion.•The TiO2 crystals exhibit facet-dependent photo-response and photocatalytic efficiency.Anatase TiO2 microcrystals with exposed (001) facet were fabricated by the hydrothermal treatment of TiF4, using NH4HF2 as the auxiliary capping reagent. The morphology of the products as well as the exposure of (001) facet was tuned by simply controlling the concentration of F− ion. The TiO2 microcrystals exhibited facet-dependent photo-response and photocatalytic performance. The sample with higher percentage of exposed (001) facet had extended photo-response and higher efficiency for the degradation of Acid Red dye under UV irradiation.