Recently, great attention has been directed towards the fabrication of solar-driven nanophotocatalysts for wastewater treatment. Thus, in this work, CeO2-based nanoheterostructures were synthesized by mixing n-type CeO2 nanoparticles (NPs) with p-type Cu2S and n-type Ag2S NPs to form Cu2S/CeO2 (p–n) and Ag2S/CeO2 (n–n) nanoheterostructures, respectively. The synthesis of pristine CeO2 and CeO2-based nanoheterostructure architectures and their characterization is conducted using XRD, XPS, TEM, HRTEM, UV–Vis, N2 sorpometry, and electrochemical techniques. Pristine CeO2 NPs had a particle size of 3.9 nm and a surface area of 72.40 m2 g−1, which increased with the generation of nanoheterostructures to 12.3 and 11.1 nm and to 81.5 and 101.16 m2 g−1 for Cu2S/CeO2 and Ag2S/CeO2, respectively. Moreover, both nanoheterostructures showed strong levels of visible light absorbance relative to UV absorber pristine CeO2 NPs. Moreover, Mott-Schottky measurements were collected to determine electrochemical flat potential and band gap structures, and based on the derived results, a schematic diagram of the separation of electron–hole and insight into mechanistic routes involved are given. The photocatalytic degradation of rhodamine 6G (R6G) under natural sunlight was investigated. Based on changes in the temporal UV–Vis spectra of R6G observed over time, photocatalytic efficiencies were estimated at 23%, 44% and 30% for pristine CeO2, Cu2S/CeO2 and Ag2S/CeO2, respectively. The enhancement of the photocatalytic performance of the nanoheterostructures was attributed to the generation of p–n and n–n heterojunction arrangements, which facilitated photogenerated charge separation and transfer.