Supporting education in rural areas is the key to supporting and helping educationally undeveloped areas to achieve high-quality development. Because it can effectively avoid the problems of low economic efficiency and weak continuity in traditional teaching, a digital form of teaching that takes advantage of information technology has gradually become a new type of teaching. How to enhance resource delivery to empower educational and teaching innovation has become a key and contentious point in the study of digital volunteer education. Based on the primary goals of promoting balanced allocation of educational resources, innovating curriculum teaching, and helping the construction of the teaching team in disadvantaged areas, this study constructs a multi-agent collaborative digital volunteer education model that is effective. This model uses collaborative participation of multiple types of relevant subjects, supported by online and offline integrated learning spaces, with the teaching community as the key, the dual-teacher live interactive teaching model as the core, and driven by evidence-based teaching and learning support services. The application of this model found that students achieved three-dimensional collaborative development in knowledge, ability, and attitude, and that the professional quality and level of local teachers were also improved. The multi-agent collaborative digital volunteer education model constructed in this study provides a reference for the innovative development of digital volunteer education.