Microporous polymers based on 1,3,5-triazine units are prepared by Friedel-Crafts reaction of 2,4,6-trichloro-1,3,5-triazine with aromatic compounds. 2,4,6-Trichloro-1,3,5-triazine is polymerized with benzene, biphenyl, and terphenyl in dichloromethane in the presence of aluminum chloride. The surface areas of the polymers are in the range of 558 to 1266 m2 g−1, depending on the aromatic linker length. At ambient pressure and temperature, the polymers exhibit high CO2 uptakes of 38–51 cm3 g−1. The CO2 uptake is significantly enhanced by 70–90% for the polymers carbonized at 400 °C for 1 h and at 800 °C for an additional 1 h under nitrogen. This result suggests that rigid microporous polymers can be used as precursor polymers for the synthesis of advanced porous carbon materials without the activation process.