Plant‐to‐plant signalling is a key mediator of interactions among plant species. Plants can perceive and respond to chemical cues emitted from their neighbours, altering survival and performance, impacting plant coexistence and community assembly. An increasing number of studies indicate root exudates as key players in plant‐to‐plant signalling. Root exudates mediate root detection and behaviour, kin recognition, flowering and production, driving inter‐ and intra‐specific facilitation in cropping systems and mixed‐species plantations. Altered interactions may be attributed to the signalling components within root exudates. Root ethylene, strigolactones, jasmonic acid, (‐)‐loliolide and allantoin are signalling chemicals that convey information on local conditions in plant–plant interactions. These root‐secreted signalling chemicals appear ubiquitous in plants and trigger a series of belowground responses inter‐ and intra‐specifically, involving molecular events in biosynthesis, secretion and action. The secretion of root signals, mainly mediated by ATP‐binding cassette transporters, is critical. Root‐secreted signalling chemicals and their molecular mechanisms are rapidly revealing a multitude of fascinating plant–plant interactions. However, many root signals, particularly species‐specific signals and their underlying mechanisms, remain to be uncovered due to methodological limitations and root‐soil interactions. A thorough understanding of root‐secreted chemical signals and their mechanisms will offer many ecological implications and potential applications for sustainable agriculture. This review deals with the roles of root exudates in plant‐to‐plant signalling, and the identity of root‐secreted chemical signals and their molecular mechanisms, providing fascinating insights into communication and interactions among plants.