In order to improve the environment-friendly steel enterprise (EFSE) dynamic competitive ability and sustainable development ability, the measures to improve collaborative operation of EFSE supply chain was put forward. The model based on game theory was built to analyze the collaborative operation process of the EFSE supply chain and the factors affecting it. Results show that keeping long-term cooperation with supply chain members, improving cooperation environment gradually, and establishing a fair and honesty assurance system are necessary to implement EFSE supply chain collaborative operation.