A synthetic route for the formation of 2-[bis(2-trifluoromethylphenyl)phosphinoylmethyl]pyridine N-oxide (1c) and 2-[bis(3,5-trifluoromethylphenyl)phosphinoylmethyl]pyridine N-oxide (1d) was developed and the new ligands characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The coordination chemistry of 1c was examined with Yb(NO3)3 and the molecular structure of one complex, [Yb(1c)(NO3)3(DMF)].DMF.0.5H2O, was determined by single-crystal X-ray diffraction methods. The ligand is found to coordinate in a bidentate fashion, and this is compared against lanthanide coordination chemistry observed for the related ligand, [Ph2P(O)CH2] C5H4NO.