Effective contact and collision between reactants and active sites are essential for heterogeneous catalysis. Herein, we investigated molecular diffusion in more than 200 kinds of zeolites, and an intriguing "diffusive skin effect" was observed, whereby molecules migrated along the pore walls of zeolites (i.e., diffusion trajectories) because of the effect of the guest-host interaction and diffusion barrier. Furthermore, it was found that such a "diffusive skin effect" of zeolites would strongly promote the contacts and collisions between reactants and active sites in the reaction process, which might effectively promote the zeolite-catalyzed performance. These new findings will provide some new fundamental understanding of zeolite catalytic mechanisms under confinement effect.