Z-Scheme　photocatalysts　as　a　research　focus　perform　strong　redox　capability　and　high　photocatalytic　performance.　WO3/KNbO3　photocatalysts　were　fabricated　by　ball　milling　method,　and　performed　higher　photocatalytic　activity　in　liquid　degradation(rhodamine　B,　methylene　blue　and　bisphenol　A),　compared　with　WO3　or　KNbO3　monomer.　This　is　due　to　that　Z-scheme　heterojunction　is　formed　between　WO3　and　KNbO3,　and　the　holes　photoexcited　in　valence　band　of　KNbO3　are　quickly　combined　with　the　electrons　in　conduction　band　of　WO3.　The　electrons　accumulated　in　conduction　band　of　KNbO3　show　high　reducibility,　thereby　reducing　O-2　to　O-center　dot(2)-,　and　the　holes　in　valence　band　of　WO3　show　high　oxidative　to　oxidize　H2O　to　(OH)-O-center　dot,　respectively.　Furthermore,　it　is　proved　by　means　of　electron　spin　resonance(ESR)　spectra,　terephthalic　acid　photoluminescence　probing　technique(TA-PL),　and　UV-Vis　absorption　spectra　of　nitroblue　tetrazolium.　This　work　indicates　that　the　fabrication　of　Z-scheme　structure　can　improve　the　photocatalytic　activity　by　efficiently　separating　the　photogenerated　electrons　and　holes　in　the　photocatalytic　reaction　system,　which　is　helpful　to　deeply　understand　the　migration　mechanism　of　photoexcited　carrier(band-band　transfer　and　Z-scheme　transfer)　in　heterojunction　photocatalysts.