The deactivation mechanism of Cu–ZnO catalyst was investigated in detail. During the glycerolhydrogenolysis cycles, the morphology of Cu–ZnO catalyst was firstly changed from sphericalnanoparticles to lamellar structure and then to rod-like structure, and the uniform surface compositionwas deteriorated. The obvious aggregation of Cu and ZnO crystallite sites led to the decrease in specificsurface area and pore volume. Furthermore, the Cu content on the catalyst surface significantlydecreased with the increase of the number of reaction cycle. These findings provide in-depth insights onthe deactivation of Cu–ZnO catalyst and the obvious decrease in glycerol conversion.