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Polyoxometalate-based metal-organic frameworks (POMOFs) with bifunctional Lewis-Brønsted acid were designed by confining polyoxometalates (POMs: phosphotungstic acid (PW), phosphomolybdic acid (PMo) or silicotungstic acid (SiW)) within the Zr-MOFs. The confined POMs not only have their own Brønsted acid, but can also regulate the Lewis acid strength of the POMOFs via charge regulation, ultimately allowing the POMOFs to display superior catalytic performance in the tandem catalysis of furfural (FAL) to γ-valerolactone (GVL). Among the three catalysts (POMOF-PW, POMOF-PMo and POMOF-SiW), a complete conversion of FAL was achieved, while POMOF-PW exhibited the highest GVL yield (58.1 %) at 160 °C within 23 h. The leaching experiment and structural characterization of the catalyst before and after recycling confirmed the stability of the catalyst structure. The humin originates from the polymerization of furan ring-containing compounds driven by Brønsted acid. The adsorption configuration of the substrate molecules on the catalyst offers a new explanation for the tandem reaction process, i.e. that perpendicular adsorption performs only the first step of the tandem reaction, while the coexistence of perpendicular and horizontal adsorption permits the entire reaction process. This work gives unique insights into the tandem reaction of FAL and can guide the design of efficient tandem reaction catalysts. A synthetic strategy has been developed to construct polyoxometalate-based metal-organic framework (POMOF) with bifunctional Lewis-Brønsted acid sites by chemically confining polyoxometalates (POM) in metal-organic framework (MOF) channels. Confined POM not only endows the catalyst with Brønsted acid sites, but also enhances the acid strength of the catalyst through charge regulation, which finally promotes the catalyst to exhibit excellent catalytic performance in the multi-step cascade catalysis from furfural (FAL) to γ-valerolactone (GVL). This work also provides insight into the origin and driving sites of the by-product humin, as well as the role of the adsorption configuration in the catalytic process. A look into the future of the multi-step tandem reaction of FAL to GVL is presented. [Display omitted] [ABSTRACT FROM AUTHOR]