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We have successfully constructed electron-rich Bi and Mo species with a highly degree of dispersion and hierarchical pore texture by introducing Cu/SiO 2 as a bi-functional modifier for MoO 3 -Bi 2 SiO 5 /SiO 2 . Characterization techniques suggest the Bi species was modified by Cu with a Bi-OÀ 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/SiO 2 with Bi 2 SiO 5 /SiO 2 support.