Adsorption　and　activation　of　C-H　bonds　by　photocatalysts　are　crucial　for　the　efficient　conversion　of　C-H　bonds　to　produce　high-value　chemicals.　Nevertheless,　the　delivery　of　surface-active　oxygen　species　for　C-H　bond　oxygenation　inevitably　needs　to　overcome　obstacles　due　to　the　separated　active　centers,　which　suppresses　the　catalytic　efficiency.　Herein,　Ni　dopants　are　introduced　into　a　monolayer　Bi2WO6　to　create　cascaded　active　units　consisting　of　unsaturated　W　atoms　and　Bi/O　frustrated　Lewis　pairs.　Experimental　characterizations　and　density　functional　theory　calculations　reveal　that　these　special　sites　can　establish　an　efficient　and　controllable　C-H　bond　oxidation　process.　The　activated　oxygen　species　on　unsaturated　W　are　readily　transferred　to　the　Bi/O　sites　for　C-H　bond　oxygenation.　The　catalyst　with　a　Ni　mass　fraction　of　1.8%　exhibits　excellent　toluene　conversion　rates　and　high　selectivity　towards　benzaldehyde.　This　study　presents　a　fascinating　strategy　for　toluene　oxidation　through　the　design　of　efficient　cascaded　active　units.