The substoichiometric isotope dilution analysis for U(VI) in a synergic extraction system of an excess amount of a chelating agent HHFA and a substoichiometric amount of neutral ligand TOPO has been developed. A constant but substoichiometric amout of U(VI) can be precisely extracted, and U down to ppm levels can be accurately determined by the present method. This method was applied to the analysis of a phosphate rock.