A methodology of using chloroacetylated polystyrene resin (PS‐COCH2‐Cl) to initiate the ring‐opening polymerization of oxazolines was established to prepare highly amininated polystyrene (PS) resin beads for CO2 adsorption. The structure of the resulting material was fully characterized by FTIR, BET, TGA, and XPS, and the results suggested that the chloroacetyl group was more reactive in initiating the ring‐opening polymerization of oxazolines than the known chloromethyl groups, which eliminated the use of iodide salts that are costly. The resulting material could adsorb CO2 at an equilibrium adsorption capacity of 3.15 mmol/g at 25°C and 1 atm, and the adsorption isotherms conformed to the Freundlich isothermal model, indicating a multi‐layer adsorption type. Kinetic study suggested that the adsorption was predominantly governed by chemical interactions with physical adsorption playing a supportive role. For a simulated flue gas of 15% CO2/N2, 50°C, relative humidity of 80%, SO2 concentration of 50 ppm, the adsorption performance of PS‐COCH2‐LPEI was even improved and the capacity can be well retained for at least 20 adsorption–desorption cycles, demonstrating a promising application prospect of this solid polyamine material in removing CO2 from flue gas.