A polymer foam material with both the open‐cell porous structure and the polyethylenemine (PEI)‐grafted inner face was constructed for CO2 capture. The porous poly(tert‐butyl acrylate) foam was first prepared via a concentrated emulsion polymerization, and then the carboxyl groups were introduced on the interface of porous polymer after the hydrolysis reaction. Subsequently, the surface of the foam was grafted with PEI, and finally the PEI‐grafted porous polymer foam designed as a CO2 capture material was obtained. The structures of the foams were characterized by infrared spectroscopy, EDS, and SEM. The CO2 adsorption properties were measured by adsorption/desorption cycles. As a result, the polymer foam contained a large number of amine groups (13.9 wt % N), and therefore possessed a high CO2 adsorption capacity (5.91 mmol g−1 at 40°C and 100 kPa). In addition, they also exhibited high CO2 adsorption rate, good selectivity for CO2‐N2 separation, and good stability according to CO2 cyclic adsorption/desorption test. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47844.