Educational institutions are envisioned as principal agents for addressing the current sustainability challenge that society is facing. Education for Sustainable Development (ESD) is transformational and concerns learning content and outcomes, pedagogy and the learning environment in itself. ESD entails rethinking the learning environment (physical and virtual) in line with sustainable development, which implies classrooms' transformation towards learner engagement, formative assessments and active methodologies. This paper responds to this need through exploring the relationship between Smart Classrooms and four widely used ESD methodologies (project or problem-based learning, case study, simulation and cooperative inquiry), identifying how the dimensions and categories of the characteristics of Smart Classrooms can contribute and lead to the implementation of ESD methodologies in real teaching practice in an effective way. The method used in this study consisted of a literature review of both theoretical frameworks separately, ESD and Smart Classrooms, and a subsequent expert analysis to identify the interrelation between both. The Smart Classroom shows a high level of adequacy for using problem and project-based learning, case study and cooperative inquiry methods because of its characteristics in terms of technology developments, environmental conditions and processes. Simulation is the ESD methodology with the lowest level of adequacy in a Smart Classroom, because it is primarily held online rather than through face-to-face teaching. Smart Education facilitates the putting in practice of ESD processes as it enables the creation of intelligent, sustainable, resource-efficient, personalised and adaptive learning environments. Further empirical research is needed to explore the influence that the Smart Classroom has in enabling ESD processes and practices, and to identify students' and teachers' needs at different education levels. Additionally, teacher training programmes focused on the correct use of Smart Classrooms and on the digital competence of teachers are critical to its successful implementation.