ZnO nanostructures were grown on the stainless steel mesh substrates using an aqueous chemical growth method. The different additives (such as 1,3-diaminopropane and polyethyleneimine) can be used to control the morphology of ZnO nanostructures. ZnO nanowires exhibit very prominent green emission and week UV emission from defect and band gap in the cathodoluminescence spectrum, respectively. The different morphology of ZnO nanostructures on the stainless steel mesh substrates can be used to irradiate UV light for the photocatalytic degradation of four kinds of organic pollutants, such as methylene blue, rhodamine 6G, methyl orange, and 4-nitrophenol. The ZnO nanowires can provide a higher surface-to-volume ratio and stronger defect emission, resulting in their highest photocatalytic performance in 10 W UV light irradiation. The ZnO nanowire arrays on the stainless steel mesh substrates provide a large-scale, facile, low-cost, high surface area, and high photocatalytic efficiency, which shall be of significant value for practical applications of the decomposition of environment pollutants and reusing of wastewater treatment.