The twenty-first century’s society experiences new challenges in being immersed in a new paradigm of the educational system. Higher education institutions should train professionals so that they are able to experience real situations in order to encourage reflection on affective, aesthetic, and ethical dimensions of these people in their relations with the natural and sociocultural environment. Learning strategies must allow the acquisition of creative, active, and applied knowledge as well as the development of critical thinking. According to the experiential learning theory, to achieve this, higher education should use student-centered interactive and collaborative teaching methodologies and focus studies on the skills that graduates must have, promoting student know-how, initiative, and autonomous learning. Business simulations are instruments that fulfil the above characteristics, facilitating learning. The objective of this research was to provide a model that identifies the determining factors (simulation’s realism and structure, perceived usefulness, and students’ learning motivation) in the effectiveness of using these tools to develop critical thinking focused on sustainability. Three hundred and twenty-six surveys completed by undergraduate students were obtained, which used a structural equation model (SEM) to analyze the influence of realism, simulation structure, perceived usefulness, and students’ motivations to develop critical thinking. The outcomes according to the experiential learning theory showed that the game’s realism lets students perceive its usefulness and, together with an adequate simulation structure, determines the students’ learning motivations by developing critical thinking.