Green leaf volatiles (GLVs) are six-carbon volatile oxylipins ubiquitous in vascular plants. GLVs are produced from acyl groups in the biological membranes via oxygenation by a pathway-specific lipoxygenase (LOX) and a subsequent cleavage reaction by hydroperoxide lyase. Because of the universal distribution and ability to form GLVs, they have been anticipated to play a common role in vascular plants. While resting levels in intact plant tissues are low, GLVs are immediately synthesized de novo in response to stresses, such as insect herbivory, that disrupt the cell structure. This rapid GLV burst is one of the fastest responses of plants to cell-damaging stresses; therefore, GLVs are the first plant-derived compounds encountered by organisms that interact with plants irrespective of whether the interaction is competitive or friendly. GLVs should therefore be considered important mediators between plants and organisms that interact with them. GLVs can have direct effects by deterring herbivores and pathogens as well as indirect effects by attracting predators of herbivores, while other plants can recruit them to prepare their defenses in a process called priming. While the beneficial effects provided to plants by GLVs are often less dramatic and even complementary, the buildup of these tiny effects due to the multiple functions of GLVs can amass to levels that become substantially beneficial to plants. This review summarizes the current understanding of the spatiotemporal resolution of GLV biosynthesis and GLV functions and outlines how GLVs support the basic health of plants.