AbstractSingle‐molecule optoelectronics offers opportunities for advancing integrated photonics and electronics, which also serves as a tool to elucidate the underlying mechanism of light‐matter interaction. Plasmonics, which plays pivotal role in the interaction of photons and matter, have became an emerging area. A comprehensive understanding of the plasmonic excitation and modulation mechanisms within single‐molecule junctions (SMJs) lays the foundation for optoelectronic devices. Consequently, this review primarily concentrates on illuminating the fundamental principles of plasmonics within SMJs, delving into their research methods and modulation factors of plasmon‐exciton. Moreover, we underscore the interaction phenomena within SMJs, including the enhancement of molecular fluorescence by plasmonics, Fano resonance and Rabi splitting caused by the interaction of plasmon‐exciton. Finally, by emphasizing the potential applications of plasmonics within SMJs, such as their roles in optical tweezers, single‐photon sources, super‐resolution imaging, and chemical reactions, we elucidate the future prospects and current challenges in this domain.