Structurally characterized hexacoordinate organophosphorus compounds remain rare due to their highly reactive nature and thermal instability. Herein we report the first synthesis of a pair of O-facial and O-meridional hexacoordinate oxaphosphates (5B and 5D) obtained from the O-apical and O-equatorial β-hydroxyalkylphosphoranes 3 and 4. This was achieved by using the bulky C2F5-groups on the ortho-substituted aryl backbone. Calculations of the relative energies of possible isomers indicate 5B and 5D are thermodynamic products. Although the mechanisms of their formation and the determining factor of stereo-selectivity are still unclear, their isolation and structure conformation contributes to a formulation of a viable strategy for diastereoselective synthesis of heteroleptic hexacoordinate organophosphates.