Hierarchical MoO2 hollow microspheres have been successfully fabricated on a large scale through a convenient hydrothermal reductive process. MoO2 hollow microspheres are composed of subunits (nanospheres or nanoplates), which are actually self-aggregated by hundreds of tiny primary nanoparticles. BET nitrogen adsorption reveals that the MoO2 hollow microspheres have mesoporous shell with pore size of 5-20 nm. Reaction parameters, such as mole ratio of reactant, reaction temperature and time, were discussed in detail. Center-hollowing evolution process induced by Ostwald ripening was proposed to explain the formation mechanism of hierarchical MoO2 hollow microspheres. The adsorption ability of MoO2 hollow microspheres was evaluated by adsorbing Cr (VI) at room temperature. The experimental results indicated that MoO2 absorbent displayed higher adsorption capacity compared to activated carbon, which would be potential application in wastewater treatment. (C) 2014 Elsevier Ltd. All rights reserved.