Endowed with rich structural diversity and tunable functionalities, metal-organic frameworks (MOFs) have become appealing candidates in diverse applications. Nonetheless, many existing MOFs possess varying degrees of chemical instability in some extreme conditions, which significantly hampers their practical applications. Herein, we successfully fabricated a series of MOFs/parylene-N hybrid materials by introducing a parylene-N layer onto the exterior surface of MOFs via the chemical vapor deposition technique. Strikingly, the shielding layer not only imparts the chemical stability of MOFs without obviously impacting their inherent nature but also makes the coated MOFs possess outstanding catalytic performance in water-mediated organic reactions. Such an integrated system might open a new window for MOFs to broaden the scope of real-world application in harsh aqueous environments.