The synthesis and characterization of two 1,2‐azaborine‐containing phosphine ligands are described. The structural and electronic parameters of the two ligands were compared with those of their direct all‐carbon analogues using X‐ray crystallography and UV‐photoelectron and IR spectroscopy. Our results indicate that the azaborine‐containing ligands are significantly stronger electron donors than their corresponding carbonaceous counterparts, while the steric parameters remain similar.