A gas bubble-templating method has enabled synthesis of a diverse portfolio of hollow transition-metal sulfides microspheres (e.g., CdS, ZnS, CuS and Bi2S3) by a general one-step route. The products were characterized by X-ray powder diffraction, scanning and transmission electron microscopy, high-resolution transmission electron microscopy, energy dispersive spectroscopy analysis, N2 adsorption and UV–vis diffuse reflectance spectroscopy. The shell of all hollow spheres is composed of single-crystal metal sulfide nanoparticles and the shell thickness can be readily controlled by changing the deposition time. These hollow microspheres are envisioned to have broad applications in catalysis, Li-ion batteries, microreactors, biomedicines, etc. As an example, here, we demonstrate that the prepared CdS and ZnS hollow sub-micrometer spheres are excellent photocatalysts with higher photodegradation efficiency of potential polluting agents than that of commercial CdS, ZnS and TiO2 P25 under visible light and UV light illumination, respectively.