This article describes the synthesis and characterization of microporous organic copolymers (PP-N-x, where “x” is the molar percent of triphenylamine) prepared from triphenylamine and dichloro-p-xylene using a combination of oxidative polymerization and Friedel–Crafts alkylation process promoted by anhydrous FeCl 3 . The samples possessed BET specific surface areas from 318 to 1530 m 2 g −1 with the increasing content of dichloro-p-xylene. The highest CO 2 uptake of 4.60 mmol g −1 was observed for PP-N-25, which was one of the highest values among MOPs reported to date under these conditions. The polymers possessed stable and reversible CO 2 adsorption–desorption performance in at least 5 consecutive runs without noticeable deterioration of CO 2 uptake capacities.