The synthesis and spectroscopic properties of the neutral metal(III) heteroleptic porphyrin-phthalocyanine double-decker sandwich-like complexes (TPP)M(III)(Pc) (1) are reported (TPP and Pc = dianions of tetraphenylporphyrin and phthalocyanine, respectively; M = La, Pr, Nd, Eu, Gd, Er, Lu, and Y). The electron transfer reactions of these M(III) complexes are presented. They undergo up to four reversible one-electron transfers in nonaqueous media. The spectroscopic properties of these (TPP)M(III)(Pc) (1) sandwich-like derivatives are consistent with the presence of a one-electron-oxidized pi-radical phthalocyanine ring, Pc(.-), as a ligand. Accordingly, these pi-radical complexes 1 yield monoanionic species (TPP)M(III)(Pc)(-) 2 upon reversible one-electron reduction and di-pi-radical complexes (TPP)M(III)(Pc)(+) 3 containing a tetraphenylporphyrin pi-radical and a phthalocyanine pi-radical ligand upon reversible one-electron oxidation. In the neutral complexes 1 and the di-sc-radical derivatives 3, the energies of the near-infrared bands are linearily correlated with the ionic radii r(i) of the tervalent central metals.