ABSTRACTAmino‐functionalized hollow microporous organic nanospheres (NH2‐HMONs) were successfully synthesized by a combination of hyper‐crosslinking mediated self‐assembly process and a post‐modification strategy. Benefiting from amino groups and hollow microporous structure, the resultant NH2‐HMONs can be used to immobilize Pd nanoparticles (Pd@NH2‐HMONs) and enhance the adsorption capacity for iodine. The obtained Pd@NH2‐HMONs exhibited outstanding catalytic activity for hydrogenation of nitroarenes to aniline analogues. This strategy represents a new method for the preparation of porous organic polymers with special morphologies and functionalizations for potential applications including adsorption, separation, and catalysis. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2045–2052