Personal values and attitudes can help to explain food choice. This study confirmed a hierarchical organization of the value–attitude–behavior chain: Food-related values influence attitudes, and these, in turn, impact behavior. Contrary to previous findings, values are only partially mediated by attitudes: Some food-related values are fully mediated, whereas others are partially mediated, and still others have exclusively direct effects on purchase behavior. Questionnaire data from a roughly representative sample of 851 adults living in Switzerland was complemented with actual food purchase behavior measured by a loyalty card of a Swiss retailer over the period of one year. Four theoretically derived structural equation models were compared across eight different food product categories (organic, fair trade, low-budget, fresh convenience, ready-to-eat, light, functional foods, fruits and vegetables). The results question central assumptions of the theory of planned behavior and emphasize the role of food-related values in food consumption. Implications for marketing and future product developments of food companies are discussed.