We have achieved substitutional doping of ullazine with either two BO units or with one BO unit and one BN unit. The synthesis of these B-doped ullazines is straightforward, using demethylation and borylative cyclization as the key steps. Ullazine cores of both BN/BO-ullazines (2) and bis-BO-ullazines (3) are very close to being planar. Their electronic and photophysical properties were investigated by ultraviolet-visible, fluorescence spectroscopy, cyclic voltammetry, and density functional theory calculations.