Di-or trialkyl phosphite reacted with tellurium(IV) chloride in methylene chloride at room temperature to give dialkyl chlorophosphate and elemental tellurium within a 10 minute. This reaction might proceed through penta-coordinate dihaplophosphite intermediate [$(RO)_3PCl_2$] which is immediately converted into dialkyl chlorophosphate by dealkylhalogenation. When tellurium(IV) chloride and trialkyl phosphite was reacted with nucleophiles such as alcohol and amine, the phosphorylation of nucleophiles readily occurred to give corresponding dialkyl organophosphates.