Water-dispersible monodisperse hollow Fe3O4 microspheres were prepared via a one-pot hydrothermal process based on FeCl3 center dot 6H(2)O, sodium citrate, urea and sodium polyacrylate (PAAS). Different alkali sources and FeCl3 center dot 6H(2)O amounts were added to investigate the formation mechanism, and a gas-bubble-assisted Ostwald ripening process was possibly responsible for the formation of hollow structure. In the process, the particle size and morphology could be effectively controlled by the slight change of FeCl3 center dot 6H(2)O addition amount. Meanwhile, monodisperse solid microspheres were obtained when sodium acetate was added to offer alkaline environment. The microspheres exhibited superparamagnetic properties with high saturation magnetization value about 76.7 emu.g(-1), at room temperature, and the BET surface area of the sample was 50.04 m(2).g(-1). Besides, it was found that the particles could be used for constructing photonic crystals. Such monodisperse hollow Fe3O4 microspheres have a great application potential in biomedicine, MRI agents and color display areas. (C) 2014 Elsevier B.V. All rights reserved.