Polyene hydrocarbons and epoxides are used as pheromone components and sex attractants by four macrolepidopteran families: the Geometridae, Noctuidae, Arctiidae, and Lymantriidae. They constitute a second major class of lepidopteran pheromones, different from the C10-C18 acetates, alcohols, and aldehydes commonly found in other species. They are biosynthesized from diet-derived linoleic or linolenic acids and are characterized by C17-C23 straight chains, 1-3 cis double bonds separated by methylene groups, and 0, 1, or 2 epoxide functions. Pheromone blends are created from components with different chain lengths, numbers of double bonds, and functional groups, or from mixtures of epoxide regioisomers or enantiomers, with several examples of synergism between enantiomers. Behavioral antagonists also limit interspecific attraction, with numerous examples of antagonism by enantiomers. This review summarizes the taxonomic distribution, mechanisms used to generate unique pheromone blends, and the identification, synthesis, and biosynthesis of these compounds.