There have been extensive efforts to synthesize crystalline covalent triazine-based frameworks (CTFs) for practical applications and to realize their potential. The phosphorus pentoxide (P O )-catalyzed direct condensation of aromatic amide instead of aromatic nitrile to form triazine rings. P O -catalyzed condensation was applied on terephthalamide to construct a covalent triazine-based framework (pCTF-1). This approach yielded highly crystalline pCTF-1 with high specific surface area (2034.1 m  g ). At low pressure, the pCTF-1 showed high CO (21.9 wt % at 273 K) and H (1.75 wt % at 77 K) uptake capacities. The direct formation of a triazine-based COF was also confirmed by model reactions, with the P O -catalyzed condensation reaction of both benzamide and benzonitrile to form 1,3,5-triphenyl-2,4,6-triazine in high yield.