Graphyne, a theorized carbon allotrope possessing only sp‐ and sp2‐hybridized carbon atoms, holds great potentials in many fields, especially in catalysis and energy‐transfer/storage devices. Using a bottom‐up strategy, we synthesized a new N‐doped graphyne analogue, triazine‐ and 1,4‐diethynylbenzene‐based graphyne TA‐BGY, in solution in gram‐scale. The unique sp/sp2 carbon‐conjugated TA‐BGY possesses an extended porous network structure with a BET surface area of approximately 300 m2 g−1. Owing to its low optical band gap (1.44 eV), TA‐BGY was expected to have many applications, which were exemplified by the photodegradation of methyl orange and photocatalytic bacterial inactivation.