Brönsted acid and metal nanoparticles are important catalytic functional groups. In this work, a bifunctional heterogeneous catalyst with both strong Brönsted acid and metal nanoparticles was prepared. First Brönsted acid groups were obtained by sulfonating graphene oxide, next metal organic frameworks MIL‐101 (Cr) grew on sulfonated graphene oxide (SGO), then palladium nanoparticles (NPs) were encapsulated in MIL‐101@SGO composites. The catalyst was characterized by a variety of different techniques including XRD, SEM, TEM, EDS, FT‐IR, TGA, and nitrogen physisorption measurements. Tandem heterogeneous catalysis of Pd@MIL‐101@SGO was investigated for the one‐pot direct conversion of styrene into β‐alkoxy alcohol. The catalyst retained high catalytic activity after 5 times of reuses in aqueous solutions. No loss of crystal structure was detected by PXRD and no leakage of Pd was detected by ICP‐AES. Therefore, Pd@MIL‐101@SGO proved to be an effective recyclable heterogeneous catalyst for synthesizing β‐alkoxy alcohol and exhibited potential application in industry.

Porous organic polymer (POP) coated on a metal–organic framework (MOF) has the functions and advantages of MOF and POP at the same time and has excellent catalytic ability. In this study, an efficient dual-functional core–shell composite MOF@POP with Lewis acid and Brønsted base sites was synthesized using the impregnation method in which MIL-101­(Cr) was the core component and polymelamine formaldehyde (PMF) was the shell component. Most importantly, the obtained MIL-101­(Cr)@PMF showed perfect catalytic activity in the deacetalization–Knoevenagel tandem reaction. In addition, it could still maintain ultrahigh physical and chemical stability.