Complete and partial O-functionalization of the octahydroxytetramethyl[1(4)]metacyclophane with phosphoryl groups has been carried out, and reversible intramolecular addition of hydroxy or trimethylsilyloxy groups to the neighbouring P=O bonds with the formation of spirophosphorane fragments has been shown to be typical of the 3,10,17,24-tetrahydroxy(tetrakistrimethylsiloxy)-5,12,19,26-tetrakis-o-phenylenephosphoryloxy-1,8,15,22-tetramethyl [1(4)]metacyclophane.