Among the molecular building blocks used for the construction of light-powered, electroactive ensembles, subphthalocyanines (SubPcs) hold a privileged position due to their outstanding photophysical properties. These singular cone-shaped, aromatic molecules show a strong absorption in the 550-650 nm region with excitation energies above 2.0 eV, high fluorescence quantum yields, a rich redox chemistry, and low reorganization energies. As part of our systematic investigation in the preparation and study of novel SubPc-based D–A systems, we decided to use 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) as partner for SubPcs. Thus, a 1,1,4,4-tetracyanobuta-1,3-diene (TCBD)-aniline moiety has been introduced, for the first time, at the axial position of two subphthalocyanines (SubPcs) peripherally substituted with hydrogen (H₁₂SubPc) or fluorine atoms (F₁₂SubPc). Single-crystal X-ray analysis of both SubPc-TCBD-aniline systems showed that each conjugate is a racemic mixture of two atropisomers resulting from the almost orthogonal geometry adopted by the axial TCBD unit, which were separated by chiral HPLC.