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Heterobimetallic Ln(III)–Pd(0) complexes (Ln = Y, Sm, Gd, Yb) featuring tetranuclear structures with COD as bridges were obtained via the metallation of tris(phosphinoamido) rare-earth metal complexes [Ph2PNAd]3Ln (Ad = adamantyl) with (COD)Pd(CH2SiMe3)2. Notably, the Sc(III)–Pd(0) complex possesses a C3-symmetry with a very short Sc–Pd bond length of 2.432(2) Å, while the tetranuclear complexes exhibited versatile structures both in solution and in the solid state. Reduction of the trivalent complex (Ph2PNAd)3Yb with one equivalent of KC8 in the presence of 18-c-6 afforded the divalent complex [(Ph2PNAd)3Yb][(18-c-6)K(THF)2], which was further reacted with (Ph3P)4Pd to form the first Yb(II)–Pd(0) complex. The Pd(0) → Yb dative interaction weakened significantly from Yb(III) to Yb(II) based on computational studies, which was attributed to the attenuated Lewis acidity of the Yb(II) center. Reactions of Ln(III)–Pd(0) complexes (Ln = Sc and Yb) with the disulfide PhSSPh showed that the Pd(0) center served as a two-electron donor while the reaction apparently occurred on the Ln(III) centers to form Ln(III)–Pd(0) bis-sulfide complexes. [ABSTRACT FROM AUTHOR]