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© 2020 by the authors. Licensee MDPI, Basel, Switzerland. For decades, higher education institutions have been incorporating sustainability principles. Spanish universities have considered it important that sustainability principles are integrated into the university curriculum, in order to contribute to the education of socially-responsible professionals. The present research aims to estimate pre-service educators’ awareness of selected challenges posed by Sustainable Development Goal 4 (SDG 4), and it identifies the learning experiences that contribute the most to these students’ awareness of quality education. Moreover, the study aims to explore the potential of the use of the vignettes approach for the evaluation of students’ awareness. The study drew on a sample of n = 202 first year students pursuing education-related degrees at a Spanish university. The data was collected using a vignette survey, and the data analysis was conducted using quantitative and qualitative techniques. The results show a high degree of awareness within the context of most of the challenges posed by SDG 4 and, in the search for the factors that contributed to the degree of awareness in the students, personal interests and classes taken at the university stand out. In addition, the study provides the methodological implications of the use of the vignette approach in the assessment of students’ awareness. This paper discusses the practical implications for universities of the integration of Education for Sustainable Development (ESD) competences into the curriculum.