Organoantimony(III) and organobismuth(III) phosphates (LM)(3)(PO4)(2) [M = Sb (3) and Bi (4)], containing the NCN-chelating ligand L [L = 2,6-(CH2NMe2)(2)C6H3], were prepared by the simple treatment of parent oxides 1 and 2 with H3PO4. Both compounds were characterized by elemental analysis, electrospray ionization mass spectrometry, and IR and NMR spectroscopy and in the case of 3 by X-ray diffraction techniques. Compound 3 has an interesting behavior in solution, i.e., the formation of two possible conformational isomers, which was studied by H-1, C-13, and P-31 NMR spectroscopy.