At present, coal enterprises generally have inadequate environmental protection, serious social issues, and poor corporate governance. Against the background of sustainable development strategies and the “carbon peaking” and “carbon neutrality” targets, there is an urgent need to conduct a performance evaluation of the sustainable development of coal enterprises. Environmental, social, and governance (ESG) performance is the foundation and booster of sustainable and high−quality development of coal enterprises. It is a typical application of sustainable development and performance evaluation theory to carry out ESG−led performance evaluation and case research of coal enterprises. Therefore, in this paper, we construct the model framework of ESG–grounded theory–entropy method–cloud model to research the performance evaluation of coal enterprises under the guidance of sustainable development from the dimensions of theoretical optimization and case analysis. The model framework includes the factor structure model, performance evaluation index system, index weighting model, and performance evaluation model. First, on the basis of the theory of ESG and triple bottom line, the finance–environment–society–governance (FESG) structural dimension model of coal enterprise performance evaluation was extracted through the three-level coding of grounded theory (GT). On this basis, the performance evaluation index system from the perspective of sustainable development was constructed. Second, on the basis of the entropy method (EM), the weight model of the coal enterprise performance evaluation index was constructed to determine the weight of indexes at all levels. Third, the performance evaluation model was constructed on the basis of the cloud model (CM), and the principles and methods of “dividing index grade, normalizing index grade, calculating index grade membership degree, and evaluating enterprise performance grade” were clarified. Fourth, in order to verify the feasibility of the model framework, a typical listed company (enterprise Z) in the coal industry was selected in order to conduct a case research based on the statistical data from 2016 to 2020 and analyze the performance grade evaluation results. The research shows that (1) the FESG structural dimension model extracted by grounded theory analysis method and the performance evaluation index system of coal enterprises oriented by sustainable development enrich the connotation and extension of ESG theory; (2) the index weighting model based on the entropy method can objectively determine the weight of indicators at all levels of each dimension of performance; (3) the construction path of coal enterprise performance evaluation model based on cloud model can be used to construct performance evaluation models for other industries; (4) the model framework based on the ESG–grounded theory–entropy method–cloud model can be used to reasonably measure the performance level of coal enterprises and provide theoretical support for the research of performance evaluation inside and outside the industry; (5) the sustainable development performance of coal enterprises is the basis and guarantee for achieving sustainable and high-quality development. The research results can provide theoretical reference for the regulatory authorities to formulate performance evaluation policies from the perspective of sustainable development.