CuO/CeO2　is　a　promising　catalyst　for　water–gas　shift　(WGS)　reaction　in　H2　production.　Much　effort　has　been　devoted　to　improving　its　catalytic　activity　and　stability　by　CeO2　support　modification　or　introduction　of　secondary　active　species.　Here　a　method　to　enhance　the　catalytic　performance　by　controlling　the　deposition　rate　of　copper　is　reported.　The　nature　of　CuO　and　CuO-CeO2　synergetic　interaction　are　modulated　by　using　different　copper　sources　(Cu(NO3)2　and　Cu[(NH3)]2+4)　and　controlling　reaction　temperatures.　The　as-prepared　CuO-CeO2　catalysts　show　distinguish　catalytic　performances　for　the　WGS　reaction.　The　one　prepared　by　using　Cu[(NH3]2+4)　at　the　reaction　temperature　of　30　°C　(CuCe-30N)　shows　superior　catalytic　activity　and　stability.　The　CuCe-30N　catalyst　possesses　the　largest　Cu0　surface　area　(39.2　m2g-1cat)　and　strongest　CuO-CeO2　synergetic　interaction.　The　largest　Cu0　surface　area　provides　the　most　active　sites　for　CO　adsorption　thus　leading　to　its　highest　activity.　The　strong　synergetic　interaction　prevents　Cu　crystallites　from　sintering　during　the　WGS　reaction,　thus　improving　its　thermal　stability.　©　2018　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim