A large number of scientific investigations are needed for developing a sustainable solid sorbent material for precombustion CO capture in the integrated gasification combined cycle (IGCC) that is accountable for the industrial coproduction of hydrogen and electricity. Keeping in mind the industrially relevant conditions (high pressure, high temperature, and humidity) as well as good CO/H selectivity, we explored a series of sorbent materials. An all-rounder player in this game is the porous organic polymers (POPs) that are thermally and chemically stable, easily scalable, and precisely tunable. In the present investigation, we successfully synthesized two nitrogen-rich POPs by extended Schiff-base condensation reactions. Among these two porous polymers, exhibits high CO uptake capacity at 30 bar pressure (57.2, 18.7, and 15.9 mmol g at 273, 298, and 313 K temperatures, respectively). CO/H selectivities of and at 25 °C are 434.35 and 477.93, respectively. On the other hand, at 313 K the CO/H selectivities of and are 296.92 and 421.58, respectively. Another important feature to win the race in the search of good sorbents is CO capture capacity at room temperature, which is very high for (15.61 mmol g at 298 K for 30 to 1 bar pressure swing). High BET surface area and good mesopore volume along with a large nitrogen content in the framework make an excellent sorbent material for precombustion CO capture and H purification.