A sextuple-decker heteroleptic phthalocyanine heterometallic compound (1) with a subunit arrangement of {(Pc)Sm(Pc)Cd(Pc*)Cd(Pc*)Cd(Pc)Sm(Pc)} has been prepared and analyzed using various spectroscopic instruments, in which four unsubstituted phthalocyanine anions (Pc) and two substituted analogues (Pc*) with n-pentoxyl substituents at eight peripheral positions are connected through the complexation of two Sm(III) and three Cd(II) ions. In particular, its sextuple-decker structure has been disclosed by the single-crystal X-ray diffraction technique. The solution and gel glass forms of this compound display third-order nonlinear optical properties due to the intrinsic conjugated nature over the sextuple-decker sandwich complex.