Abstract 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 2 O 5 )‐catalyzed direct condensation of aromatic amide instead of aromatic nitrile to form triazine rings. P 2 O 5 ‐catalyzed condensation was applied on terephthalamide to construct a covalent triazine‐based framework ( p CTF‐1). This approach yielded highly crystalline p CTF‐1 with high specific surface area (2034.1 m 2 g −1 ). At low pressure, the p CTF‐1 showed high CO 2 (21.9 wt % at 273 K) and H 2 (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 2 O 5 ‐catalyzed condensation reaction of both benzamide and benzonitrile to form 1,3,5‐triphenyl‐2,4,6‐triazine in high yield.