The implementation of an Environmental Management System (EMS) ISO 14001 is an instrument for achieving a corporate's sustainable development and therefore is an important tool for environmental management. Due to rapid economic development, the coating industry is increasing rapidly, resulting in several environmental problems. Many coating firms have adopted EMS; however, quantitative and qualitative evaluations of the environmental performance of EMS have rarely been examined in the literature. This paper proposed an environmental performance evaluation system that enables quantitatively assess the effects of EMS in the coating industry. A four-level framework was structured with 74 indicators and sub-indicators according to the context and characteristics of the coating industry. Divided into two aspects, the legislative system and environmental management performance system, these indicators and sub-indicators covered almost every element of ISO 14001. And the evaluation criteria were closely referred to Chinese coating industry standards and cleaner production regulations. Using analytical hierarchy process and fuzzy membership degree analysis, the weight of each indicator was determined, and evaluation results were achieved. Moreover, using a coating firm in Shanghai as a case study, this paper investigated the impacts of EMS implementation in two successive years after the firm was granted an ISO14001 certificate in 2007. The results indicated that the environmental performance of EMS in the coating firm was satisfactory in 2008, and there was an obvious improvement in 2009, which strongly demonstrated that the evaluation model was scientific and practical. Finally, further improvements are proposed from four aspects, including thoroughly identifying environmental factors, encouraging the development of advanced pollution control technologies, sustaining the improvement process of EMS after the initial adoption, and supporting the involvement of software applications.