Abstract: Speciation analysis is one of the frontiers of environmental analytical chemistry. It has strict requirement for sample preparation. Solid-phase microextraction(SPME) is a new technology of solvent-free alternative for sample preparation developed from 1990. SPME has the advantages of simplicity,fast speed, easy to automate and less risk of contamination. This new sample pretreatment technology is a promising method for speciation analysis. Applications of SPME to the speciation analysis of organo-element compounds in recent years have been reviewed in this paper.