Chemical interactions in plants often involve plant allelopathy and allelobiosis. Allelopathy is an ecological phenomenon leading to interference among organisms, while allelobiosis is the transmission of information among organisms. Crop failures and low yields caused by inappropriate management can be related to both allelopathy and allelobiosis. Therefore, research on these two phenomena and the role of chemical substances in both processes will help us to understand and upgrade agroecosystems. In this review, substances involved in allelopathy and allelobiosis in plants are summarized. The influence of environmental factors on the generation and spread of these substances is discussed, and relationships between allelopathy and allelobiosis in interspecific, intraspecific, plant–micro‐organism, plant–insect, and mechanisms, are summarized. Furthermore, recent results on allelopathy and allelobiosis in agroecosystem are summarized and will provide a reference for the future application of allelopathy and allelobiosis in agroecosystem.