Plants produce an array of oxylipins implicated in defense responses against various stresses, with about 600 oxylipins identified in plants to date. Most known oxylipins are the products of lipoxygenase (LOX)-mediated oxygenation of polyunsaturated fatty acids. One of the most well-characterized oxylipins produced by plants is the hormone jasmonic acid (JA); however, the function of the vast majority of oxylipins remains a mystery. One of the lesser-studied groups of oxylipins is comprised of ketols produced by the sequential action of LOX, allene oxide synthase (AOS), followed by non-enzymatic hydrolysis. For decades, ketols were mostly considered mere by-products of JA biosynthesis. Recent accumulating evidence suggests that ketols exhibit hormone-like signaling activities in the regulation of diverse physiological processes, including flowering, germination, plant–symbiont interactions, and defense against biotic and abiotic stresses. To complement multiple reviews on jasmonate and overall oxylipin biology, this review focuses specifically on advancing our understanding of ketol biosynthesis, occurrence, and proposed functions in diverse physiological processes.