In summary, we have developed an iron-catalyzed aza-annulative π-extension strategy with alkynes through direct C-H activation. The strategy catalyzed by an iron/trisphosphine catalyst integrates the use of oxime ether as both an auxiliary for C-H activation and an internal oxidant serving as the nitrogen source, and an isobutyl aluminum catecholate reagent as a base. This efficacious AAPE approach is compatible with a broad scope of oxime ethers seamlessly derived from readily available conjugated 5 carbonyl compounds with a variety of alkynes. The expeditious synthesis of π-extended aza-arenes facilitates discoveries in the realm of electronic materials with distinguished electronic and optical properties, as evidenced by the synthesized Heli-BCIQ as a prospective CPL material, as well as ABPhen and DNPA derivatives which showed remarkable emissive properties with narrow emission bands. These findings add new repertoires to our ongoing efforts using iron-catalysis to explore conjugated materials, 10 opening avenues for future development in both materials science and iron-catalyzed C-H activation methodology.