How to improve the energy efficiency of refineries has become an urgent issue to be solved as demand for refined products increases. It is very important to improve the energy efficiency in order to promote the sustainable and coordinated development of the economy, energy and environment. Based on the analysis of the factors that influence the energy efficiency of oil refineries, this paper constructs an index system of energy efficiency evaluation of oil refineries, and uses the combination weighting method to determine the final weights of the indexes. Then, an energy efficiency evaluation method for refinery enterprises based on grey correlation technique for order preference by similarity to an ideal solution (TOPSIS) are established. At the same time, using the production data of eight refineries, the efficiency evaluation system of the oil refinery is tested. The empirical results show that the index system can objectively and effectively reflect the energy efficiency of refineries, and can be widely used to evaluate the energy efficiency of refineries.