In this paper, we report the preparation of gamma-Fe2O3 and Fe3O4 magnetic hierarchically nanostructured hollow microspheres by a solvothermal combined with precursor thermal conversion method. These gamma-Fe2O3 and Fe3O4 magnetic hierarchically nanostructured hollow microspheres were constructed by three-dimensional self-assembly of nanosheets, forming porous nanostructures. The effects of experimental parameters including molar ratio of reactants and reaction temperature on the precursors were studied. The time-dependent experiments indicated that the Ostwald ripening was responsible for the formation of the hierarchically nanostructured hollow microspheres of the precursors. gamma-Fe2O3 and Fe3O4 magnetic hierarchically nanostructured hollow microspheres were obtained by the thermal transformation of the precursor hollow microspheres. Both gamma-Fe2O3 and Fe3O4 hierarchically nanostructured hollow microspheres exhibited a superparamagnetic property at room temperature and had the saturation magnetization of 44.2 and 55.4 emu/g, respectively, in the applied magnetic field of 20 KOe. Several kinds of organic pollutants including salicylic acid (SA), methylene blue (MB), and basic fuchsin (BF) were chosen as the model water pollutants to evaluate the removal abilities of gamma-Fe2O3 and Fe3O4 magnetic hierarchically nanostructured hollow microspheres. It was found that gamma-Fe2O3 hierarchically nanostructured hollow microspheres showed a better adsorption ability over SA than MB and BF. However, Fe3O4 hierarchically nanostructured hollow microspheres had the best performance for adsorbing MB. (c) 2012 Elsevier Inc. All rights reserved.