Accelerating the deep integration of industry-university-research has become a key link in school-enterprise collaborative education, which is an important initiative to deepen collaborative innovation among enterprises, universities, and research institutes and to promote the high-quality cultivation of talents. The article establishes an all-around collaborative education model of government, university, and enterprise association, and constructs a framework of university-enterprise collaborative case base with the technical support of AI platform and the Internet. To enhance the application feasibility of the university-enterprise collaborative case database, the nearest neighbor method is adopted for case retrieval, and the case feature attributes are obtained through local similarity, combined with global similarity for matching and retrieval of similar cases. Based on the collaborative case library between universities and enterprises, a teaching experiment was designed. The construction of the case library and its teaching effect were verified using the social network analysis method. The time consumed in case retrieval through Manhattan similarity is only about 1.5s. The network density of the online learning community based on a collaborative case between a university and an enterprise is 0.274. The average distance and cohesion index between learners are 2.003 and 0.576, respectively. The collaborative case base between universities and enterprises can improve students’ learning attitudes, enhance students’ learning interests, and provide a new avenue for cultivating high-quality talents that meet the needs of enterprises.