The interaction of SbClnBr6‐n− (n = 1—6) with various bπ‐donors has been investigated by means of UV spectroscopy, conductometry, and polarography. The influence of the bπ‐donor structure, of the corresponding cation, the ligands of the antimonates, and the solvent on the behaviour of complex formation is discussed. With increasing ionization potential of the bπ‐donor the CT absorption shifts to higher energies. Derivatives of aminobenzene lead to the formation of radical cations. The influence of 18‐crown‐6 on the radical cation formation is also discussed. With increasing content of bromine in the antimonate the overall acceptor strength increases as well. The influence of the solvent on CT energy depends on both the specific solvation of the ground state of the electron donor‐acceptor complex and the dielectric solvation of the excited state of the complex.