The straightforward synthesis and detailed characterization of nine substituted triarylformazanate boron difluoride complexes is reported. The effect of electron-donating (p-anisole) and electron-withdrawing (p-benzonitrile) substituents on optical and electrochemical properties, relative to phenyl substituents, was studied at two different positions within the formazanate ligand framework. Each of the BF2 complexes was characterized by H-1, C-13, B-11, and F-19 NMR spectroscopy, cyclic voltammetry, infrared spectroscopy, UV-vis absorption and emission spectroscopy, mass spectrometry, and elemental analysis. Select examples were studied by X-ray crystallography, revealing highly delocalized structures in the solid state. The complexes were reversibly reduced in two steps electrochemically to their radical anion and dianion forms. The complexes also exhibited substituent-dependent absorption and emission properties, accompanied by significant Stokes shifts, with the aryl substituents at the 1,5-positions of the formazanate backbone having a greater influence on these properties than aryl substituents at the 3-position. Breaking the symmetry in three different complexes resulted in a modest increase in emission intensity relative to that of symmetrically substituted derivatives.