Phosphoenolpyruvate (PEP) plays a key role in the development of plants and exists in a wide variety of species. Research on the metabolic activities of PEP in plants has received increasing attention. PEP regulates multiple processes in plant growth and development. This article provides a comprehensive summary of these pathways, including embryo formation, root development, synthesis of secondary metabolites, and the formation of lignification. We also summarize new findings, including PEP’s role in nodule energy sensing and carbon allocation under the influence of ozone. This review displays the complex and differential regulatory pathways in plant growth and development and provides a reference for basic and applied research on PEP metabolism in plants.