The poor hydrostability of most reported metal-organic frameworks (MOFs) has become a daunting challenge in their practical applications. Recently, MOFs combined with multifunctional polymers can act as a functional platform and exhibit unique catalytic performance; they can not only inherit the outstanding properties of the two components but also offer unique synergistic effects. Herein, an original porous polymer-confined strategy has been developed to prepare a superhydrophobic MOF composite to significantly enhance its moisture or water resistance. The selective nucleation and growth of MOF nanocrystals confined in the pore of PDVB-vim are closely related to the structure-directing and coordination-modulating properties of PDVB-vim. The resultant MOF/PDVB-vim composite not only produces superior superhydrophobicity without significantly disturbing the original features but also exhibits a novel catalytic activity in the Friedel-Crafts alkylation reaction of indoles with trans-β-nitrostyrene because of the accessible sites and synergistic effects.