Artificial　Z-scheme　photocatalytic　systems,　inspired　by　natural　photosynthesis,　have　been　widely　employed　for　pollutant　removal.　In　this　study,　we　fabricated　a　ternary　Z-scheme　Bi2O3/Bi/porous　carbon　nitride　(PCN)　heterojunction　with　an　intimately　coupled　interface　through　a　simple　EG-assisted　solvothermal　approach　to　improving　photocatalytic　performance　of　NO　oxidation.　The　in-situ　generated　metallic　Bi　acts　as　an　electron　mediator,　effectively　accelerating　the　separation　and　transfer　of　photoexcited　carriers.　The　unique　Z-scheme　charge　transfer　mechanism　provides　the　strong　redox　abilities　and　isolates　the　active　sites　for　specific　reactions,　thus　promoting　photocatalytic　NO　oxidation　activity.　As　a　result,　the　optimized　Bi2O3/Bi/PCN　sample　achieved　a　NO　removal　efficiency　of　94.6%,　outperforming　single-component　catalysts　and　most　previously　reported　heterojunction-based　photocatalysts.　Additionally,　in-situ　Fourier　transform　infrared　spectroscopy　was　employed　to　propose　the　NO　removal　mechanism,　offering　valuable　insight　into　the　conversion　pathway.　Such　a　heterogeneous　Z-scheme　photocatalytic　system　with　a　strong　redox　ability,　high　charge-separation　efficiency,　and　longterm　stability,　demonstrates　significantly　enhanced　photoactivity　for　pollutant　removal　and　is　expected　to　attract　increasing　interest　for　other　photocatalytic　applications.