International trade in food knows no borders, hence the need for prevention systems to avoid the consumption of products that are harmful to health. This paper proposes the use of multicriteria risk prevention tools that consider the socioeconomic and institutional conditions of food exporters. We propose the use of three decision-making methods—Technique for Order Preference by Similarity to the Ideal Solution (TOPSIS), Elimination et Choix Traduisant la Realité (ELECTRE), and Cross-Efficiency (CE)—to establish a ranking of countries that export cereals to the European Union, based on structural criteria related to the detection of potential associated risks (notifications, food quality, corruption, environmental sustainability in agriculture, and logistics). In addition, the analysis examines whether the wealth and institutional capacity of supplier countries influence their position in the ranking. The research was carried out biannually over the period from 2012–2016, allowing an assessment to be made of the possible stability of the markets. The results reveal that suppliers’ rankings based exclusively on aspects related to food risk differ from importers’ actual choices determined by micro/macroeconomic features (price, production volume, and economic growth). The rankings obtained by the three proposed methods are not the same, but present certain similarities, with the ability to discern countries according to their level of food risk. The proposed methodology can be applied to support sourcing strategies. In the future, food safety considerations could have increased influence in importing decisions, which would involve further difficulties for low-income countries.