There have been extensive efforts to synthesize crystalline covalent triazine‐based frameworks (CTFs) for practical applications and to realize their potential. The phosphorus pentoxide (P₂O₅)‐catalyzed direct condensation of aromatic amide instead of aromatic nitrile to form triazine rings. P₂O₅‐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 m² g⁻¹). At low pressure, the pCTF‐1 showed high CO₂ (21.9 wt % at 273 K) and H₂ (1.75 wt % at 77 K) uptake capacities. The direct formation of a triazine‐based COF was also confirmed by model reactions, with the P₂O₅‐catalyzed condensation reaction of both benzamide and benzonitrile to form 1,3,5‐triphenyl‐2,4,6‐triazine in high yield.