Our group recently reported their efficient light-driven synthesis 20 and promising applications as semiconductors when heteroannulated, and NFAs in OSCs when multimerized. Herein, we prepared AzaBPDIs and BACDs presenting hydroxy groups in vicinity of their ortho position. Their ortho Oannulation offers planar electron-deficient materials, showing an increase of fluorescence and a deepening of their LUMO levels. Their ability to accept electrons and their strong absorption of visible light have been used to prepare organic field effect transistors (OFETs) and OSCs, revealing that O-annulated electron-deficient materials are worth investigating to design new high-performance materials for organic electronics.