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As a new environmental management tool, the research and practice of Enterprise environmental performance evaluation are still at an early stage. The study of Power Generation Enterprise's environmental performance evaluation index system can provide universal evaluation theory for power generation enterprise environmental performance. According to the characteristics of power generation enterprise and its environmental pollution status, this paper establishes appropriate environmental performance evaluation index system, which involves two categories: basic indicators and reference indicators. And the article proposes promoting application recommendations of index system; it helps power generation enterprise improve environmental performance, forms the core competitiveness of enterprises and achieves sustainable economic development.