Phytochemical investigation of Lycium shawii Roem. & Schult provided fourteen compounds, including lyciumate (1), dehydrocostus lactone (2), costunolide (3), catechin (4), lyciumaside (5), emodin (6), (11), nonacosane-10-ol (12), betulinic acid (13) and β-sitosterol glucopyranoside (14). The compounds may be classified as three sesquiterpene lactones (1-3), two phenolic compounds (4 and 5), six anthraquinones (6-11), one long chain alcohol (12), one lupane-type triterpenoid (13) and a steroid (14). Compounds 2, 3, 7 and 9-12 are reported here for the first time as isolated from any species of Lycium as well as from the Solanaceae family while compounds 8, 13 and 14 are reported to be found for the first time in the genus Lycium. All structural assignments were made by comparing the NMR spectral data of the pure isolates with that published in the quoted literature.