A simple and template-free solution phase synthesis method has been developed for the preparation of novel CdS hollow microspheres using cadmium nitrate and thioacetamide precursors. In this manuscript, we demonstrate that process parameters such as the reaction time, precursor ratio, and reaction temperature strongly influence the morphology of the final product. The synthesized products have been characterized by a variety of methods, including X-ray powder diffraction (XRD), Raman spectroscopy, high-resolution scanning electron microscopy (HR-SEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray diffraction (EDX) analysis, X-ray photoelectron spectroscopy (XPS), and UV-visible diffused reflectance spectroscopy (UV-DRS). XRD analysis confirmed the cubic structure of the CdS microspheres, which has also been further supported by Raman spectroscopy. The HR-SEM measurements revealed the spherical morphology of the CdS microspheres which has been evolved by the oriented aggregation of the primary CdS nanocrystals. The TEM measurements confirmed the hollow shell-like structure of the spheres; the formation of their hollow interiors can be explained by the Ostwald ripening mechanism. UV-DRS studies showed that the band gap of the CdS microspheres increased with increasing cadmium-nitrate-to-thioacetamide ratio. Furthermore, studies of photocatalytic activity revealed that the synthesized CdS hollow microspheres exhibit an excellent photocatalytic performance in rapidly degrading methyl tert-butyl ether (MTBE) in aqueous solution under visible-light illumination. These results suggest that CdS microspheres will be an interesting candidate for photocatalytic detoxification studies under visible light radiation.