A facile, self‐sacrificing template route has been developed to synthesize spinel MIIIn2S4 (MII = Mn, Zn, Cd, Fe, Co, Ni) and MIIn5S8 (MI = Cu, Ag) porous microspheres. The BET surface areas of the products are around 70 m2 g–1. The urchin‐like In2.77S4 microspheres precursor acts as both starting material and template to confine the growth of the final products. The phase structures and morphologies of the products were characterized by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and electron diffraction. Possible formation process and growth mechanism for the porous structure are proposed based on the experimental results. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)