The hierarchical nanostructures of CdIn2S4 were selectively prepared through hydrothermal process in the presence of different surfactants. Structural study demonstrated existence of cubic spinel structure and micro structural study shown a pretty marigold flower like morphology without any surfactant. The effect of surfactants on the morphology and microstructure of CdIn2S4 has been studied by using Polyvinyl pyrrolidone (PVP) and Cetyltrimethyl ammonium bromide (CTAB) as a surfactants. The CdIn2S4 bipyramids with length of 0.7-1 mu m have been obtained using PVP. Interestingly, the nanopetals (thin and transparent) of CdIn2S4 are self assembled into hollow spheres in the presence of CTAB. Considering the importance of these unique nanostructures, the growth mechanism has also been proposed. The optical properties demonstrated the band gap in the range of 2.12-2.29 eV which is well within the visible region. In this contest, photocatalytic activity for hydrogen production using the above nanostructures under visible light was also demonstrated. The prima-fascia observations shows that the bipyramidal CdIn2S4 exhibit excellent photocatalytic activity for hydrogen production (3238 mu molh(-1)) than other nanostructures. Being a nanostructured semiconductor chalcogenide with a good stability will also have potential applications in solar cells and LED. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.