Cell-free enzymatic catalysis (CFEC) is an emerging biotechnology that enabling to imitate the biological transformations in complex natural networks. This biomimetic approach allows to manufacturing industrial products such as biofuels and biochemical in a green manner. Nevertheless, the main challenge in CFEC is the poor stability, which restricts the effectiveness and lifetime of enzymes in sophisticated applications. Immobilization of the enzymes within solid carriers is considered as an efficient strategy for addressing the aforementioned obstacles. Specifically, the engineering "armor-like" porous metal-organic frameworks (MOFs) exoskeleton tightly surrounding the enzymes can not only shield the enzymes against external stimulus, but also allow the selective transport of the guest via the accessible porous network. This minireview will impart the concept of this biotechnology, MOFs-entrapped enzymes, and its cutting-edge applications.