A　series　of　CuO/ZrO2　catalysts　with　different　Cu　loadings　(4.1,　6.1　and　8.4　wt.%)　were　synthesized　by　a　deposition-precipitation　method　and　evaluated　with　the　water-gas　shift　(WGS)　reaction.　In　order　to　distinguish　the　different　supported　copper　oxide　species,　(NH4)2CO　3-leaching　process　was　conducted　on　the　three　CuO/ZrO2　catalysts.　The　parent　and　leached　catalysts　were　characterized　by　ICP-OES,　XPS,　XRD,　N2-physisorption,　N2O　titration,　UV-Vis　DRS,　H　2-TPR　and　CO-TPR.　The　results　reveal　that　three　types　of　copper　oxide　species　are　present　on　the　parent　CuO/ZrO2　catalysts:　(α)　highly　dispersed　CuO　that　is　weakly　bound　with　ZrO2;　(β)　strongly　bound　Cu-[O]-Zr　species,　which　can　not　be　leached　by　(NH　4)2CO3　solution　and　is　possibly　associated　with　the　surface　oxygen　vacancy　of　ZrO2;　(γ)　crystalline　CuO.　The　XRD　and　TEM　results　of　the　freshly　reduced　catalysts　disclose　that　the　three　types　of　CuO　species　are　transformed　into　their　corresponding　metallic　states　after　the　H2-pretreatment.　It　is　found　that　the　reaction　rate　correlates　well　with　the　amount　of　Cu-[O]-Zr　species,　indicating　the　metallic　Cu　derived　from　this　species　should　be　the　catalytically　active　copper　species　for　the　WGS　reaction.　Moreover,　CO-TPR　results　disclose　that　the　Cu-[O]-Zr　species　play　a　significant　role　in　promoting　the　reactivity　of　the　surface　hydroxyl　groups,　as　is　thought　to　be　responsible　for　the　high　WGS　activity　of　the　CuO/ZrO2　catalysts.　Copyright　©　2013,　Hydrogen　Energy　Publications,　LLC.　Published　by　Elsevier　Ltd.　All　rights　reserved.