F(64)Pc(2)Ln (1(Ln), Ln = Tb or Lu) represent the first halogenated phthalocyanine double-decker lanthanide complexes, and 1(Tb) exhibits single-molecule magnet properties as revealed by solid-state magnetometry. The fluorine substituents of the phthalocyanine rings have a dramatic effect on the redox properties of the F(64)Pc(2)Ln complexes, namely, a stabilization of their reduced states. Electrochemical and spectroelectrochemical measurements demonstrate that the 1(Tb)(-/2-) and 1(Tb)(2-/3)- couples exhibit redox reversibility and that the 1(Tb)(-), 1(Tb)(2-) and 1(Tb)(3-) species may be prepared by bulk electrolysis in acetone. Low-temperature MCD studies reveal for the first time magnetization hystereses for the super-reduced dianionic and trianionic states of Pc(2)Ln.