As an important strategic fulcrum for China’s new round of opening-up, the Hainan Free Trade Port provides broad space for achieving high-quality development with its unique policy advantages and financial resources. In this context, integrating blockchain technology into the construction of the free trade port can not only help enhance the innovation and competitiveness of the talent cultivation system but also promote the coordinated development of the real economy and the industrial system. Based on the core characteristics of blockchain technology, such as “decentralization, traceability, and high credibility”, this paper focuses on the common problems in the cultivation of composite talents in current vocational colleges, including an imperfect school-enterprise cooperation guarantee mechanism, a lack of teaching resources, weak teaching staff, and insufficient practical conditions. It proposes a new idea of introducing blockchain technology into the vocational education system. Through the research on the cultivation model of composite-skilled talents in vocational colleges in the context of “blockchain +”, this paper aims to promote the in-depth integration of vocational education in vertical and horizontal aspects, and further promote the systematic, standardized, and high-quality development of composite talent cultivation.