The reaction of the Ag(I) dimer [Ag2(η2-A)2(μ,η1:η1-A)2][TEF]2 (A = [{CpMo(CO)2}2(μ,η2-P2)]) possessing labile η2-coordinated P2 ligands with the organometallic dipnictogen compounds [{CpMo(CO)2}2(μ,η2-EE')] (E = E' = As, Sb; E = P, E' = As, Sb) represents a facile synthetic route towards unprecedented heteroleptic pnictogen-rich supramolecular complexes. This method can also be extended to the analogous Cu(I) dimer and is studied by DFT computations.