Ag and Ni/ZnO photocatalyst nanostructures were successfully synthesized by a sol–gel method. In this work, the photocatalyst sample was systematically studied based on several factors affecting the performance of photocatalyst, which are size, morphology, band gap, textural properties and the number of active sites presence on the surface of the nanocatalyst. X-ray diffraction revealed that Ag/ZnO nanomaterials experienced multiple phases, meanwhile for Ni/ZnO the phase of nanomaterials were pure and single phase for stoichiometry less than 5%. Field emission scanning electron microscope (FESEM) showed almost all of the synthesized nanomaterials possessed a mixture of nanorods and spherical-like shape morphology. The Ag/ZnO showed high photocatalytic activity, producing at least 14th trials of nanocatalyst reusability on degradation of methyl orange under UV irradiation. Interestingly, this phenomenon was not observed in larger surface area of Ni/ZnO nanomaterials which supposedly favour photocatalytic activity, but instead producing poor photocatalytic performance. The main reasons were studied and exposed by temperature-programmed desorption of carbon dioxide (TPD–CO 2 ) which showed that incorporation of Ag into ZnO lattice has enhanced the number of active sites on the surface of the nanocatalyst. Whereas incorporation of Ni in ZnO has lowered the number of active sites with respect to undoped ZnO. Active sites measurement is effective and significant, providing opportunities in developing an intensive study as an additional factor.