AbstractHordeum spontaneum, wild barley, is the direct progenitor of domestic barley, Hordeum vulgare, an economically important ingredient of animal feed, beer, soy sauce, and more recently, of nutraceuticals. Domestic barley has also been used in the past as a medicine. Barley is a rich source of tocotrienols, with α‐tocotrienol being the most prevalent. Wild barley seeds were harvested from ecogeographically diverse areas across the Fertile Crescent, and the tocopherol (α–δ) and tocotrienol (α–δ) contents were determined. Diversity differences in individual and total ‘tocol’ values were significant between and within specific countries, and were significantly correlated with temperature. Wild barley may be used in the future to improve functional qualities of domestic barley. ‘Tocolome’ and ‘tocolomics’ are proposed to encompass all tocols and potentially synergy‐enhancing ‘entourage’ compounds that may occur in tocols' ‘metabolomic neighborhoods’, aiding the standardized manufacture of complex barley derivatives for nutraceutical and pharmaceutical functions.