Solving the increasing contamination from toxic heavy metal ions in wastewater is an imperative issue in photocatalysis research area. In this study, three-dimensional (3D) porous SrTiO3 microspheres have been fabricated by a sol-gel-templating method using the agarose gel bead containing SrCO3 granules as the template. The resultant SrTiO3 microspheres, several tens of micrometers in diameter, exhibit a bimodal pore structure, in which the macropore about 70-150 nm in size stems from SrCO3 granules and the mesopore about 3 nm is formed via removing the agarose fiber embedded in the composite microspheres. The porous framework of SrTiO3 microspheres is assembled by regular single-crystalline SrTiO3 nanocubes with an edge length of 100 +/- 10 nm. The highly interconnected porous network renders numerous pathways for the rapid mass transport, strong adsorption of reactants and multi-reflection of incident light. Moreover, the as-prepared SrTiO3 microspheres exhibit excellent photocatalytic performance for the Cr(VI) reduction under simulated sunlight, which can reduce nearly 100% Cr(VI) at pH 2 within 2 h and retain a relatively high reduction ability after six recycles. (C) 2016 Elsevier B.V. All rights reserved.