The σ-arsolyl complex [Mo(AsC4Me4)(CO)3(η-C5H5)] serves as a metallo-ligand for the strategic construction of μ-arsolido bridged heterobimetallic complexes [MoCr(μ-AsC4Me4)(CO)8(η5-C5H5)], [MoMn(μ-AsC4Me4)(CO)5(η5-C5H5)(η5-C5H4Me)], [MoAu(μ-AsC4Me4)(C6F5)(CO)3(η5-C5H5)] and [MoFe(μ-AsC4Me4)(CO)5(η5-C5H5)2]PF6via reactions with [Cr(THF)(CO)5], [Au(C6F5)(THT)], [Mn(THF)(CO)2(η5-C5H4Me)] and [Fe(THF)(CO)2(η5-C5H5)]PF6, respectively. The reaction of [Mo(AsC4Me4)(CO)3(η-C5H5)] with [Co3(μ3-CH)(CO)9] affords the tetrametallic species [MoCo3(AsC4Me4)(μ3-CH)(CO)11(η-C5H5)]. Crystallographic and computational data for all products are discussed.