In this paper, we reported the successful synthesis of hollow hemispherical Mn-11(HPO3)(8)(OH)(6) super-structures on a large scale via a facile mixed-solvothermal route without assistance of any surfactant, employing MnAc2 center dot 4H(2)O and NaH2PO2 center dot H2O as the reactants, the mixture of N,N-dimethylformamide (DMF) and water as the solvent. The reaction was carried out at 160 degrees C for 12 h. HPO32- ions were provided via the dismutation reaction of H2PO2-ions. The as-obtained product was characterized by X-ray powder diffraction (XRD), energy dispersive spectrometry (EDS) and field emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Some factors influencing the morphology of the hollow hemispherical Mn-11(HPO3)(8)(OH)(6) superstructures, such as the reaction temperature, time, the amount of NaH2PO2, and the volume ratio of DMF/water, were systematically investigated. A possible growth mechanism was proposed based on experimental results. (C) 2010 Elsevier B.V. All rights reserved.