Water　gas　shift　reaction　is　an　important　process　in　hydrogen　production　from　carbon-based　materials.　Cu-based　catalysts　are　widely　used　in　low-temperature　water　gas　shift　reactions.　The　problem　is　that　Cu　species　are　prone　to　sintering　and　deactivation,　as　well　as　the　controversial　reaction　mechanism.　Herein,　CuFe2O4　modified　with　Al3+　is　served　as　the　Cu-based　catalyst　precursor,　and　the　catalytic　structure-activity　relationship　as　well　as　reaction　mechanism　are　carefully　investigated.　The　modification　of　CuFe2O4　precursor　by　Al3+　enhances　the　Cu　species　dispersion,　redox　properties　and　electron　transfer　ability,　leading　to　increasing　the　proportion　of　Cu+/　(Cu0+Cu+),　which　results　in　enhancing　the　ability　of　the　catalyst　to　adsorb　CO　and　dissociate　H2O.　The　combination　of　temperature-programmed　surface　reaction　(TPSR)　and　infrared　spectroscopy　shows　that　the　catalyst　with　weak　water　dissociation　ability　and　medium　CO　adsorption　capacity　are　prone　to　obey　the　association　mechanism.