A series of ternary sulfide hollow structures have been successfully prepared by a facile glutathione (GSH)-assisted one-step hydrothermal route, where GSH acts as the source of sulfur and bubble template. We demonstrate the feasibility and versatility of this in situ gas-bubble template strategy by the fabrication of novel hollow structures of MIn2S4 (M = Cd, Zn, Ca, Mg, and Mn). Interestingly, with the reaction time varying, the hierarchical CdIn2S4 microspheres with controlled internal structures can be regulated from yolk–shell, smaller yolk–shell (yolk–shell with shrunk yolk), hollow, to solid. Under visible-light irradiation, all of our prepared CdIn2S4 samples with different morphologies were photoactivated. In virtue of the appealing hierarchical hollow structure, the yolk–shell-structured CdIn2S4 microspheres exhibited the optimal photocatalytic activity and excellent durability for both the X3B degradation and H2 evolution, which can be ascribed to the synergy-promoting effect of the small crystallite size together with the unique structural advantages of the yolk–shell structure. Thus, we hypothesize that this proof-of-concept strategy paves an example of rational design of hollow structured ternary or multinary sulfides with superior photochemical performance, holding great potential for future multifunctional applications.