Two novel nitrogen-rich aminal linked porous organic polymers, NRAPOP-O and NRAPOP-S, have been prepared using a single step-one pot Schiff-base condensation reaction of 9,10-bis-(4,6-diamino-S-triazin-2-yl)benzene and 2-furaldehyde or 2-thiophenecarboxaldehyde, respectively. The two polymers show excellent thermal and physiochemical stabilities and possess high porosity with Brunauer–Emmett–Teller (BET) surface areas of 692 and 803 m2 g−1 for NRAPOP-O and NRAPOP-S, respectively. Because of such porosity, attractive chemical and physical properties, and the availability of redox-active sites and physical environment, the NRAPOPs were able to effectively remove Cr(VI) from solution, reduce it to Cr(III), and simultaneously release it into the solution. The efficiency of the adsorption process was assessed under various influencing factors such as pH, contact time, polymer dosage, and initial concentration of Cr(VI). At the optimum conditions, 100% removal of Cr(VI) was achieved, with simultaneous reduction and release of Cr(III) by NRAPOP-O with 80% efficiency. Moreover, the polymers can be easily regenerated by the addition of reducing agents such as hydrazine without significant loss in the detoxication of Cr(VI).