Nerium indicum is an ornamental plant that is widely distributed in tropical and subtropical regions, and it has many kinds of bioactive components which are closely related to pharmacological and toxicological effects. In this paper, the chemical constituents in the leaves of N. indicum were analyzed by GC-MS and LC-MS, respectively. The relative content of each component was calculated by peak area normalization method. Sixty-six volatile constituents were identified from the leaves of N. indicum. The main constituents were phytol (10.02%), n-hexadecanoic acid (5.99%), and squalene (2.90%). Meanwhile, forty-eight compounds were identified from the polar phase extract of N. indicum leaves. Moreover, silica gel column and polyamide column chromatography were used, and three compounds were separated and purified from the methanol extract of N. indicum. With the aid of nuclear magnetic resonance technology, the three chemicals were identified as quercetin 3-O-robinobioside (1), rutin (2) and oleandrin (3), respectively, in which quercetin 3-O-robinobioside was isolated from N. indicum for the first time. The results are of great significance for the further utilization of the N. indicum resources.