To better understand the stability of isolable primary phosphine oxides, new members of this family were synthesized through the oxidation of the corresponding phosphines. Specifically, the previously reported air‐stable primary phosphines (R)‐2‐phosphanyl‐2’‐methoxy‐1,1’‐binaphthyl, 9,10‐dihydro‐9,10‐etheno‐anthracen‐9‐yl phosphine, and 3‐phosphino‐2‐naphthol were treated with hydrogen peroxide or meta‐chloroperoxybenzoic acid to yield the new primary phosphine oxides. The compounds were characterized using NMR, MS, EA, and X‐ray crystallography. The oxides were further investigated in thermal disproportionation, and studied as ligands in half‐sandwich Ru(II) complexes bearing an auxiliary η6‐p‐cymene ligand.