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Human factors are intrinsically involved at virtually any level of most industrial/business activities, and may be responsible for several accidents and incidents, if not correctly identified and managed. Focusing on the significance of human behaviour in industry, this article proposes a multi-criteria decision-making (MCDM)-based approach to support organizational risk assessment in industrial environments. The decision-making trial and evaluation laboratory (DEMATEL) method is proposed as a mathematical framework to evaluate mutual relationships within a set of human factors involved in industrial processes, with the aim of highlighting priorities of intervention. A case study related to a manufacturing process of a real-world winery is presented, and the proposed approach is applied to rank human factors resulting from a previous organisational risk evaluation from which suitable inference engines may be developed to better support risk management.