Porous ZnIn2S4 microspheres have been successfully synthesized by means of a facile thermal solution method at 353 K. This method was a simple route that involved low temperature, no templates, no catalysts, no surfactants, or organic solvents. Scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, nitrogen sorption analysis, and a UV-vis spectrophotometer were used to characterize the products. The results demonstrated that the microspheres, which were composed of many ZnIn2S4 single crystal nanosheets, underwent the Oswald ripening and self-assembly processes. A morphology formation mechanism has been proposed and discussed. The porous ZnIn2S4 product showed an enhancing visible-light photocatalytic activity for methyl orange degradation. The as-grown architectures may have potential applications in solar energy conversion, environmental remediation, and advanced optical/electric nanodevices.