ZrO2 carriers with different crystalline phase structures were prepared, including monoclinic phase (m-ZrO2), tetragonal phase (t-ZrO2) and amorphous phase (a-ZrO2), then Cu/m-ZrO2, Cu/t-ZrO2, and Cu/a-ZrO2 catalysts were prepared by sedimentation method and applying for synthesis of iminodiacetic acid by dehydrogenation of diethanolamine to testing theirs performance. The structures of the catalysts were characterized by XRD, Nitrogen-physical adsorption desorption, XPS, H2-TPR and CO2-TPD. The results show that Cu/ m-ZrO2 catalysts interface is more conducive to the stable existence of Cu+/Cu0, with more alkaline sites and better oxidation resistance. In the dehydrogenation reaction of diethanolamine, Cu/m-ZrO2 catalyst had better performance, the reaction time was reduced from 5 h to 2.5 h, and the yield of iminodiacetic acid was 97.64%.