The role of 2-Furyl phosphines as ligands for transition-metal-mediated organic synthesis was discussed. The steric and electronic properties of phosphorus(III) ligands with emphasis on phosphines bearing the 2-furyl group were analyzed. It was found that Stille coupling with tri-2-furylphosphine (TFP) ligand allows for milder reaction conditions and hence the attenuation of unwanted side reactions.