Zinc oxide and gold–zinc oxide (Au–ZnO) nanostructures with multiple rods (multipods) morphology were successfully prepared. Au–ZnO nanostructures were synthesized via a simple precipitation route method in the presence of oligoaniline-coated gold nanoparticles. The Au–ZnO catalyst obtained was applied for the degradation of methyl orange in an aqueous solution under UV irradiation. Effects of the operational parameters such as the solution pH, amount of photocatalyst, and dye concentration on the photocatalytic degradation and decolorization of methyl orange were studied. Detailed studies including kinetic study and regeneration of catalyst were carried out on the optimal conditions for the photodegradation of methyl orange by Au–ZnO multipods in aqueous solution. Effect of foreign species on the photodegradation of methyl orange was also studied. An enhancement of the photocatalytic activities for photodegradation of methyl orange was observed when the gold nanoparticles were loaded on the zinc oxide multipods. The proposed catalyst was applied for the degradation of methyl orange in synthetic wastewater samples with satisfactory results.