Shifting food choices towards sustainability entails the analysis of dietary behavior determinants. This study aimed to explain and predict the intention to follow a sustainable diet and its adoption in a representative sample of adults (n= 838) in Italy. An online survey based on the theory of planned behavior (TPB) was developed. The adoption of a sustainable diet was measured as self-perceived behavior, adherence to the Mediterranean diet (MD), and food consumption frequencies. Psychometric analysis and correlations between attitude, subjective norms, and perceived behavioral control (PBC) with both intention and behavior assessments were evaluated. Structural equation models were used to test whether and to what extent attitude, subjective norms, and PBC explained intention and behavior. Significant associations were found between TPB constructs and the behavior measures underlining the main role of intention and PBC in affecting behavior. The applied TPB models explained behavioral intention at most (78%). The results suggested promising interventions in narrowing the attitude–behavior gap to encourage specific adult population groups in Italy to adopt virtuous food consumption habits. Beside the implementation of price mechanism strategies, educational initiatives to increase awareness about food and diet sustainability issues and the reinforcement of the perceived control on food consumption at the individual level are recommended.