ZnO/V2O5 core−shell nanostructures have been prepared by a two-step synthesis route through combined hydrothermal growth and magnetron sputtering. After annealing under oxygen ambience, a ZnO/V2O5 heterogeneous lollipop-like nanoarray formed. The microstructure and crystal orientation of those nanolollipops were investigated by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM), which show single crystal structure. The optical properties were characterized by UV−vis spectroscopy and showed quite different absorption curves for the as-deposited and annealed samples. The ZnO/V2O5 nanolollipops demonstrated excellent photocatalytic activity in terms of decomposing 2,6-dichlorophenol (2,6-DCP) under visible light, indicating their promising potential as catalysts for industrial wastewater and soil pollution treatments.