The list of values (LOV) typology, which has been extensively used in personalvaluesresearch, makes the distinction between external (relations-oriented or interpersonal) and internal (self-directed––or personal––and apersonal) values. The present survey employs confirmatory factor analysis to test and validate the LOV scale in an organic food consumers’ context in Greece. The structure of the LOV scale (external and internal values) is proven to repeat itself in this context. Internal values, such as “self-respect” and “enjoyment of life” (personal and apersonal respectively), are found to be the main motivators behind the purchase of organic products in Greece, corresponding to the motives of healthiness and better taste of the organic products. Simultaneously, external (interpersonal) values, such as “belonging”, corresponding to the motive of environmental protection through organic cultivation, are deemed of lesser importance. Additionally, a value-based segmentation task identified a number of organic-consumer clusters with clear-cut LOV structure, which possibly explains their diversified attitudinal and socio-demographic profile. Finally, valuable insights are offered regarding organicconsumers’ exploratory food buying behaviour.