Selenium is a micronutrient with a wide range of functions in animals, including humans, and in microorganisms such as microalgae. However, its role in plant metabolism remains ambiguous. Recent studies of Se supplementation showed that not only does it increase the content of the element itself, but also affects the accumulation of secondary metabolites in plants. The purpose of this review is to analyze and summarize the available data on the place of selenium in the secondary metabolism of plants and its effect on the accumulation of some plant metabolites (S- and N-containing secondary metabolites, terpenes, and phenolic compounds). In addition, possible molecular mechanisms and metabolic pathways underlying these effects are discussed. It should be noted that available data on the effect of Se on the accumulation of secondary metabolites are inconsistent and contradictory. According to some studies, selenium has a positive effect on the accumulation of certain metabolites, while other similar studies show a negative effect or no effect at all. The following aspects were identified as possible ways of regulating plant secondary metabolism by Se-supplementation: changes occurring in primary S/N metabolism, hormonal regulation, redox metabolism, as well as at the transcriptomic level of secondary metabolite biosynthesis. In all likelihood, the confusion in the results can be explained by other, more complex regulatory mechanisms in which selenium is involved and which affect the production of metabolites. Further study on the involvement of various forms of selenium in metabolic and signaling pathways is crucial for a deeper understanding of its role in growth, development, and health of plants, as well as the regulatory mechanisms behind them.