ZnPd bimetallic nanoparticles supported on the Al-doped ZnO support showed efficient catalytic performance for glycerol hydrogenolysis to 1,2-propanediol (1,2-PDO). The Al species in the ZnPd/ZnO-3Al catalyst were highly related to the reaction activity of the catalysts. It was confirmed that the Al-A((IV)) species in the ZnPd/ZnO-3Al catalyst determined the reduction of ZnO, the size of ZnPd, oxygen vacancy density, and the reaction activity. Calcination temperature had significant influences on the distribution and migration of Al(IV) in ZnO lattice, and hence affected the reaction activity.