Two subphthalocyanines (SubPcs) decorated at their peripheral (SubPc 1) or peripheral and axial (SubPc 2) positions with tetracyanobuta-1,3-diene (TCBD)–aniline moieties have been prepared as novel electron donor–acceptor (D–A) conjugates. In 1 and 2, the multiple functionalization of C3-symmetric SubPcs by TCBD moieties, each of them having a chiral axis, results in the formation of several stereoisomers. Variable temperature 1H-NMR studies in chlorinated solvents suggest that these latter species, which are detected at low temperatures, rapidly interconvert – on the NMR timescale – into each other at room temperature. Beside their unique structural and stereochemical features, 1 and 2 present interesting physicochemical properties. Steady-state absorption and fluorescence, as well as electrochemical studies on 1 and 2 clearly point to an important degree of electronic communication between the SubPc, the TCBD and the aniline subunits. Moreover, in both derivatives, photoexcitation of the SubPc moiety yields charge transfer products involving the electron-rich SubPc moiety and the electron-withdrawing TCBD fragment. Interestingly, such polarized excited state species evolve in 1 and 2 in different ways. While in the former compound, it directly decays to the ground state, the fourth axial TCBD moiety in 2 leads to the formation of an intermediate fully charge separated state prior to the ground state deactivation.