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.