[(RhPPh3)6(μ3-Se)8] and [Pd6(μ3-Te)8]4−, two complexes with [M6] octahedra capped by eight μ3-Ch ligands (Ch = Se, Te), were obtained by the treatment of [Pb2Ch3]2− anions with [Rh(PPh3)3Cl] or [Pd(PPh3)2Cl2], respectively, in ethane-1,2-diamine. Both compounds comprise the first molecular [M6(μ3-Ch)8] aggregates with the respective elemental combinations. Besides syntheses and structures of the title compounds, we report quantum-chemical calculations for a deeper understanding of the electronic properties of these molecular CHEVREL-like complexes.