A new sesquiterpene, named valeriene (1), along with three iridoids, namely valepotriate (2), dihydrovaltrate (3) and acevaltrate (4) were isolated from the ethyl acetate extract of Valeriana pseudofficinalis roots. The structures of these compounds were determined by 1D and 2D NMR, MS techniques, and X-ray single crystal diffractometry. This is the first report of the chemical components isolated from this plant.Valeriana officinalis L. (Valeriana) has a distribution nearly throughout Euroasia. The roots and rhizomes of it have been used in traditional medicine as a sedative for centuries. There are about 31 species of the Valeriana genus in China. Many iridoids associated with the sedative activity have been isolated from the roots and rhizomes of species in this genus [1,2]. A new species, Valeriana pseudofficinalis C. Y. Chen, which is distinguished from V. officinalis both by its morphological and chemical characteristics, has been widely used for muscle aches and pains in China [3,4]. In this work, our investigation on the EtOAc extract from V. pseudofficinalis roots resulted in the isolation of a new sesquiterpene, named valeriene (1), along with three known iridoids, namely valepotriate (2), dihydrovaltrate (3), and acevaltrate (4). All of components were isolated from V. pseudofficinalis for the first time. This present paper describes the structure elucidation of these compounds.Valeriene (1) was isolated as a white crystal, mp 157-159°C; UV ( MeOH, λ max ): 264 nm; ES-MS (m/z): 257 [M+Na] + , 491 [2M+Na] + ; EI-MS (m/z): 234(M + ), 219 (M-CH 3 ) + . The HREIMS spectrum of 1 showed the molecular ion at m/z 234.1623, which establishes the molecular formula as C 15 H 22 O 2 (calcd 234.1620) with five degrees of unsaturation. Its 13 C NMR (Table1) and DEPT spectrum indicated the presence of 15 carbons: three methyl carbons, four methylene carbons, three methine carbons, and three quaternary carbons.The IR spectrum (KBr, 1672, 1629 cm -1 ) and its 13 C NMR (δ 193.8, 155.2, 142.8) and DEPT indicated the presence of an α,β-unsaturated aldehyde. The HMBC spectrum shows the relations of δ 9.38 with 155.2, 142.8 ppm, δ 193.8 with δ 6.71, which indicated the presence of an α,β-unsaturated aldehyde.