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Functionalized hypercrosslinked polymers (HCPs) with surface areas between 213 and 1124 m²/g based on a range of monomers containing different chemical moieties were evaluated for CO₂ capture using a pressure swing adsorption (PSA) methodology under humid conditions and elevated temperatures. The networks demonstrated rapid CO₂ uptake reaching maximum uptakes in under 60 s. The most promising networks demonstrating the best selectivity and highest uptakes were applied to a pressure swing setup using simulated flue gas streams. The carbazole, triphenylmethanol and triphenylamine networks were found to be capable of converting a dilute CO₂ stream (>20%) into a concentrated stream (>85%) after only two pressure swing cycles from 20 bar (adsorption) to 1 bar (desorption). This work demonstrates the ease with which readily synthesized functional porous materials can be successfully applied to a pressure swing methodology and used to separate CO₂ from N₂ from industrially applicable simulated gas streams under more realistic conditions.