© 2017, Springer Science+Business Media, LLC. ZrO2-decorated ZnO (ZrO2|ZnO) nanoparticles (NPs) have been synthesized by a facile co-precipitation method in the presence of cetyltrimethylammonium bromide (CTAB) surfactant. The ZrO2 amount in the NPs has been varied from 1.0, 2.0, 4.9, to 9.3% by weight. The resulting NPs are heterostructured and consist of a crystalline ZnO core (wurtzite phase) surrounded by an amorphous ZrO2 layer. X-ray diffraction analyses support this observation. The NPs show a narrow size distribution and are slightly elongated. Compared to pure ZnO NPs, the hybrid ZrO2|ZnO ones show enhanced photocatalytic activity toward the degradation of Rhodamine B under UV–Vis light. Such enhancement has been partly attributed to the increased amount of oxygen vacancies when ZrO2 is incorporated into the NPs, as shown by X-ray photoelectron spectroscopy analyses.