It is possible directly to separate and analyse, quantitatively and qualitatively, the valepotriates from Valeriana crude extracts or from commercial Valeriana preparations by high-performance liquid chromatography. The separations are achieved on 4 or 8 mm I.D. columns packed with silica gel (particle size 10 micron) with n-hexane-ethyl acetate mixtures as eluent. A refractive index detection system is necessary for determining all of the valepotriates. If the concentration differences between didrovaltratum and valtratum are very great, an ultraviolet (UV) detector must be used and the determination must be conducted in two steps. For valtratum drugs UV detection alone will suffice. As internal standards p-dimethylaminobenzaldehyde should be used for extracts and preparations from valtratum races, and benzaldehyde in the presence of didrovaltratum races. This determination is superior to the combined thin-layer chromatographic-hydroxamic acid method used hitherto with respect to time consumption, precision, and sensitivity.