Rhododendron capitatum community expansion is a major threat to alpine meadow. Allelopathy is an important mediator in managing relationships between plants in natural ecosystems. However, allelopathy and specific allelochemicals of R. capitatum have not been studied yet. In this study, the allelopathy of the foliage litter of R. capitatum was explored on Elymus nutans, Poa pratensis and Medicago ruthenica, and the chemical composition and their allelopathy were studied. The results showed that the aqueous extract of the foliage litter of R. capitatum had an allelopathy of “low concentration promotion and high concentration inhibition” on the germination of E. nutans, P. pratensis, and M. ruthenica. Organic acids, fatty acids, terpenes, phenols, and phenolic acid compounds were identified, with Zanamivir (77.81%), alpha-linolenic acid (18%), Kaurenoic acid (23.50%), 4-hydroxyphenylglycolic acid (21.54%), and Quinic acid (28.24%) having the highest relative content, and all five compounds showed significantly inhibitory effects on seed germination and seedling growth of E. nutans, P. pratensis, and M. ruthenica, which further suggests that the five compounds are the critical allelochemicals for negative allelopathy of R. capitatum. These results highlight the crucial role of inhibitory allelopathy produced by R. capitatum in the establishment and expansion of its populations.