The contribution explores the centrality of the educational relationship within care-oriented contexts, with specific reference to the long-standing collaboration between the University of Florence and the university hospital “Azienda Ospedaliera Universitaria Meyer” (AOU Meyer). The analysis focuses on Hospital Schooling and Home Education as key pedagogical arrangements designed to ensure continuity of learning for children and adolescents living with conditions of vulnerability. The educational relationship – understood both as a sphere of professional competence and as the foundational core of any formative process – is examined through its relational, emotional, and empathic dimensions. Integrating pedagogical, psychological, and neuroscientific perspectives, the chapter underscores the relevance of mentalisation and empathy in fostering the development of the educational bond, which becomes especially critical in situations marked by fragility. Personal narratives, memory, and emotions emerge as essential elements in processes of identity construction and in the enactment of educational care. Education is framed as a profoundly relational practice that demands awareness, responsibility, and reflexivity on the part of adults – parents, teachers, pedagogues, and care professionals – who accompany children throughout their learning pathways and well-being trajectories. The essay thus offers an ecosystemic perspective on educational care, providing theoretical and operational tools for understanding and supporting formative relationships within hospital-based educational contexts.