The article suggests a simple one-step sol–gel method for synthesizing nanostructured zinc oxide films co-doped with copper and aluminum. It shows the possibility of forming hierarchical ZnO:Al:Cu nanostructures combining branches of different sizes and ranks and quasi-spherical fractal aggregates. It demonstrates the use of the synthesized samples as highly efficient photocatalysts providing the decomposition of toxic dyes (methyl orange) under the action of both ultraviolet radiation and visible light. It establishes the contribution of the average crystallite size, the proportion of zinc atoms in the crystalline phase, their nanostructure, as well as X-ray amorphous phases of copper and aluminum to the efficiency of the photocatalysis process.