We　have　successfully　constructed　electron-rich　Bi　and　Mo　species　with　a　highly　degree　of　dispersion　and　hierarchical　pore　texture　by　introducing　Cu/SiO2　as　a　bi-functional　modifier　for　MoO3-Bi2SiO5/SiO2.　Characterization　techniques　suggest　the　Bi　species　was　modified　by　Cu　with　a　Bi-O−Cu　coordination　structure,　and　copper　species　became　a　capture　site　for　Mo　species　that　improved　the　dispersity　and　interface　bonding　strength　of　Mo　and　regulated　electron　structure　of　Bi　and　Mo　species,　synchronously.　Additionally,　the　hierarchical　pore　was　constructed　by　compositing　Cu/SiO2　with　Bi2SiO5/SiO2　support.　©　2020　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim