Field investigations conducted in the wild alpine rhododendron forest in the Baili Rhododendron Nature Reserve found that the natural regeneration of the forest was hindered. This paper used GC-MS to identify and analyze the most abundant chemical compounds in the leaves of four of rhododendron species (Rhododendron simsii, Rhododendron decorum, Rhododendron liliiflorum, and Rhododendron pulchrum). The results showed that the chemical substances in the four rhododendron leaf samples were mainly aldehydes, alcohols, and esters. Among them, the ester content in the leaves of R. simsii is the most abundant, the alcohol content in the R. decorum is the most abundant, and the aldehyde content in the R. liliiflorum is the most abundant. These results are conducive to the protection of the rhododendron ecosystem and laid a scientific foundation for studying the difficulties of natural regeneration of rhododendron communities.