The title compound, [Mo(C5H5)(C2H3O)(C24H27P)(CO)2], was prepared by reaction of [Mo(C5H5)(CO)3(CH3)] with tris(3,5-dimethylphenyl)phosphane. The complex exhibits a four-legged piano-stool geometry with trans-disposed acetyl and phosphane ligands. The molecular geometry is nearly identical to that of the triphenylphosphane derivative, but introduction of methyl groups on the aromatic phosphane substituents significantly impacts supramolecular organization. In the crystal, non-classical C—H...O interactions involving the acetyl carbonyl group lead to a chain motif along [010], and another set of C—H...O close contacts join inversion-related molecules.