The aim of this article is to analyze the benefits of solidarity promoted by volunteering in family education at various Spanish elementary schools which are Learning Communities. One of the common organization principles in these schools is solidarity, which is visible in various spaces and actions. Among these, volunteers of very diverse profiles are included in family education. The results presented here are part of a broader research project, 'The improvement of the educational system through the family education in vulnerable groups ' (2014-2017), funded by the State Plan for Scientific and Technical Research and Innovation of the Government of Spain. Qualitative fieldwork has been carried out in eight schools (semistructured interviews, focus groups and life stories) with families, students, teachers and volunteers from five Autonomous Communities. Among the main results, it was highlighted that volunteering contributes to strengthening the solidarity dynamics in these schools and to improving the school climate. Specifically, 1) creating more learning environments where mutual help relationships are established between volunteers and families as well as between families, 2) creating egalitarian interactions that foster friendship and trust, 3) increasing motivation and expectations of the families' training. The inclusion of volunteers in family education, especially in schools in disadvantaged environments, is contributing to the improvement of learning and motivation not only in family members, but also in children. These results offer more evidence to that already existing on factors contributing to the overcoming of educational determinism. This establishes that academic achievement is determined by the socioeconomic and educational level of families.