Abstract: Drawbacks of requiring highly selective extractants and difficulties of phase-crossing in phase separation were encountered in the conventional chemical speciation analysis.Aiming to the solution of the problems,the systematic clustering method was applied to the simultaneous determination of lead of various species in simulated geological samples,and on the base of the conventional speciation analysis with stable extraction constants,a set of standard samples with various compositional ratios of lead species were established,and analyzed by the prescribed method.As shown by the analytical results,the relative errors obtained were all less than ±11%,and better accuracy was achived by applying the systematic clustering as compared with the conventional chemical speciation analysis.The drawbacks mentioned above were overcome.