It is known that ZnO is an n-type semiconductor with photocatalytic performances under ultraviolet light irradiation. Constructing a superior structure for a modified electron band has been one of the major research goals for photocatalytic ZnO. Here we report a new technical route for making nano-ZnO coatings with a porous topographic morphology. The coatings were fabricated by plasma spraying the mixture of suspension and solution liquid precursors. Pre-loading of ZnO and Zn powders in the precursor was carried out for the purpose of tailoring the structure of the coatings. The coatings in micron thicknesses showed a porous skeleton and a fluffy top layer consisting of ultrafine ZnO grains. Photocatalytic testing by measuring the degradation of methylene blue revealed significantly enhanced activities of the coatings deposited using the ZnO/Zn loaded precursor. The hybrid-structured ZnO coatings exhibited a narrowed band gap and modified oxygen defects as compared to those deposited from the single liquid feedstock. The results shed light on a one-step easy thermal spray fabrication of polytropic nanostructured functional coatings by employing solid powder-loaded liquid as the starting feedstock.