<p>Metal-organic networks (MONs) have gained much attention due to their high surface areas and tunable structures, which underpin their potential for gas adsorption and separation. However, the stability issue remains a significant bottleneck that severely restricts their broader practical deployment. Therefore, exploring strategies to address this issue is of great significance but full of challenges. Herein, we highlight recent advances in combining MONs with polymers through surface polymerization, an approach that effectively enhances stability without sacrificing porosity, thereby enabling operation under harsher environments. Beyond stability, polymer incorporation imparts additional functions, including improved gas separation and photo-responsiveness that are inaccessible to the individual components. Finally, we propose the promising research directions of the construction of molecular sieves or stimuli-responsive functional polymer layers that leverage the merits of surface polymerization for applying MONs.</p>