Chemical constituents of the whole herb of Rhodiola kirilowii(Regl) Maxim.were investigated.The separation of the constituents was achieved by using a combination of various chromatographic techniques including column chromatography over silica gel,ODS,Sephadex LH-20 and reversed-phase HPLC.Their structures were elucidated by spectroscopic techniques including 1D and 2D NMR spectroscopy.Eleven compounds were obtained and identified as 4-hydroxyphenylethyl-(4'- methoxyphenylethyl)ether(1),1-(2-hydroxy-2-methylbutanoate)-β-D-glucopyranose(2),4-ethoxy-phenylethanol acetate(3),p-hydroxyacetophenone (4),p-hydroxy-benzoic acid ethylester(5),4-hydroxybenzoic acid(6),4-hydroxybenzaldehyde(7),R(-)-mellein (8),stigmasterol(9),4-methoxy-phenylethanol(10),and methylgallate(11).Among them,1 and 2 are new compounds; compounds 3,5,7,8,and 10 were isolated from Rhodiola genus for the first time;and compounds 4,6,9,and 11 were isolated from Rhodiola kirilowii(Regl) Maxim.for the first time.