Mixed-ligand heterometallic compounds [BiRh(O2CCF3)4-x(O2CR)x] (R = But, x = 2 (cis); R = Me, Bui, x = 1) have been obtained by gas-phase reactions of bismuth(II) trifluoroacetate with the corresponding rhodium(II) carboxylate. This synthetic approach was found to be very effective for tuning the properties and introduction of chiral ligands at a heterobimetallic core