Using hydride generation-atomic fluorescence spectrometry(HG-AFS), we analyzed the total selenium content in the medicinal parts and the forms of selenium in the rhizosphere soil in nine Chinese medicinal materials of west Hunan. Comparative analysis of the enrichment factor in the medicinal parts of the Chinese medicinal materials to explore its selenium-enriching capacity. The results showed that the contents of selenium in Fagopyrum dibotrys, Fritillaria, Rheum palmatum L., Polygonatum odoratum and Polygonatum sibiricum were decreased in the order of 1.01, 0.35, 0.25, 0.24, 0.20 mg/kg, respectively. The contents of selenium in Euphrasia pectinata Ten, Hypericum attenuatum Choisy, Liparis nervosa and Saxifraga stolonifera Curt. decreased in turn, 1.29, 1.17, 0.90, 0.54 mg/kg, respectively. All the studied Chinese herbal medicines belongs selenium-enriched and high-selenium herbal. The Fagopyrum dibotrys and the millet grass were of good selenium enrichment capacity and are suitable for the cultivation for selenium-rich Chinese herbal medicine. The total selenium content in the rhizosphere soil was 1.42 mg/kg in avaverage, which reached the standard of selenium-enriched soil. The RES-Se and OM-Se accounted for the major selenium form in the rhizosphere soil and FMO-Se, SOL-Se as well as EX-Se followed.