High yield production of micro/nanostructured nanoparticulate TiO2 microspheres (NTMs) via a facile microwave-assisted hydrothermal approach was investigated. The rapid and uniform microwave heating could reduce the reaction time to 30 min, an order of magnitude shorter than that of conventional hydrothermal methods. The characterization data confirmed that the resultant NTMs were highly uniform in size, having an average diameter of ~0.5 孮 The obtained NTMs were found to be constructed by well-crystallized anatase phase nanoparticles ranging from 5 to 10 nm that can be readily controlled by the microwave radiation temperature. Nitrogen sorption isotherm analysis revealed that the obtained NTMs possessed abundant mesoporous structures with a high specific surface area of 124 m2 g-1. An in situ self-aggregation formation process under controllable pH in presence of urea was proposed. The results obtained from the application of NTMs for simultaneous photocatalytic decontamination of Cr(VI) and methyl orange (MO) demonstrated a strong synergistic effect that dramatically enhanced both Cr(VI) reduction and MO oxidation removal efficiencies. This work not only enriched the synthesis methods of the micro/nanostructured TiO2, but also provided a new means to improve the photocatalytic efficiency via structural-induced synergistic effect, applicable to the other catalysis systems.