Abstract In industrially relevant Cu/ZnO/Al 2 O 3 catalysts for methanol synthesis, the strong metal support interaction between Cu and ZnO is known to play a key role. Here we report a detailed chemical transmission electron microscopy study on the nanostructural consequences of the strong metal support interaction in an activated high‐performance catalyst. For the first time, clear evidence for the formation of metastable “graphite‐like” ZnO layers during reductive activation is provided. The description of this metastable layer might contribute to the understanding of synergistic effects between the components of the Cu/ZnO/Al 2 O 3 catalysts.