The unique combination of a divalent organolanthanide fragment, Cp-2*Yb, with bipyrimidine (bipym) and a palladium bis-alkyl fragment, PdMe2, allows the rapid formation and stabilization of a Pd-IV tris-alkyl moiety after oxidative addition with MeI. The crucial role of the organolanthanide fragment is demonstrated by the substitution of bipym by the 4,5,9,10-tetraazaphenanthrene ligand, which drastically modifies the electronic structure and tunes the stability of the Pd-IV species.