Abstract: Object To study the chemical constituents of Cypripedium smithii L. Methods Compounds were isolated by repeated silica gel chromatographies and their structures were determined by spectral analysis. Results Five compounds were isolated from C. smithii and their structures were identified as β-sitosterol (Ⅰ), 4-hydroxybenzyl methyl ether (Ⅱ), 4-hydroxybenzyl ethyl ether (Ⅲ), batatasin Ⅰ 6-hydroxy-2, 4, 7-trimethoxyphenanthrene (Ⅳ), bis[4-(β-D-glucopyranosyloxy)-benzyl] (s)-(-)-2-sec-butylmalate (Ⅴ). Conclusion All compounds are obtained from this plant for the first time.