Abstract: With the continuous enhancement of people's environmental awareness and policy requirements as well as the increasing demand for oil, vigorously developing coal-to-oil technology is of strategic importance to ensure the energy security, adjust and optimize the energy structure of China. Focusing on the coal-to-oil refinery, considering the construction, procurement, production, transportation and sales process of the refinery, along with the related constraints such as the supply from coal production areas and market demand, the optimal mixed integer linear programming model of the coalto-oil supply chain was established with the maximum profit of the coal-to-oil refinery as the objective function, and was solved by a large-scale mathematical programming solver(Gurobi) based on the branch and bound method. The research achievement has been successfully applied to a coal-to-oil refinery in some region of China, demonstrating its great guiding significance to the construction of the site coal-to-oil supply chain. To a certain extent, it can reduce resource consumption, improve supply chain revenue and realize the efficient operation of the entire supply chain.