The novel macrocyclic compounds {(OCH2CMe2CH2O)[(S)PN-t-Bu]2}2 (4) and {(OCH2CMe2CH2O)[P(N-t-Bu)2P(1,2-O2C6Cl4)]}2·3C6H5CH3 (5·3C6H5CH3) based on the cyclodiphosphazane unit are synthesized and characterized by X-ray structure determination; their solution state NMR spectra are consistent with the solid state structures.