The synthesis of π-conjugated acceptors based on thiadiazoloquinoxaline (TQ) derivatives is described. Apart from reporting on the functionalization of the TQ core, the influence of the substituents was studied by UV−vis absorption and emission spectroscopy, cyclic voltammetry measurements, and DFT calculations. By changing the donor as well as the π-spacer, a fine-tuning of the photo- and electrochemical properties was achieved