This paper reports on the synthesis of Ce-doped ZnO (CZO) nanoparticles (NPs) by an alternative polyol method at low temperature. The method, facile and rapid, uses acetate-based precursors, ethylene glycol as solvent, and polyvinylpyrrolidone as capping agent. The effects of the Ce-doping concentration (ranging from 0 to 8.24 atomic%) on the structural, morphological, compositional, optical, luminescence, and photocatalytic properties of the NPs were investigated by several techniques. The structural findings confirmed that the CZO NPs have a typical hexagonal wurtzite-type structure with a preferred orientation along the (101) plane. The results obtained by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) revealed that the NPs size decreased (from ~30 to ~16 nm) with an increase in the Ce-doping concentration. Energy Dispersive X-Ray Spectroscopy (EDS) and High Resolution Transmission Microscopy (HRTEM) results confirmed the incorporation of Ce ions into the ZnO lattice. Ce-doping influences the photoluminescence (PL) emission compared to that of pure ZnO. The PL emission is related to the presence of different kinds of defects, which could take part in charge transfer and/or trapping mechanisms, hence playing an essential role in the photocatalytic activity (PCA). In fact, in this work we report an enhancement of PCA as a consequence of Ce-doping. In this sense, the best results were obtained for samples doped with 3.24 atomic%, that exhibited a photocatalytic degradation efficiency close to 99% after 60 min ultraviolet (UV) illumination, thus confirming the viability of Ce-doping for environmental applications.