Carbon emissions and environmental protection issues have become the pressure from the international community during the current transitional stage of China’s energy transformation. China has set a macro carbon emission target, which will reduce carbon emissions per unit of Gross Domestic Product (GDP) by 40% in 2020 and 60−65% in 2030 than that in 2005. To achieve the emission reduction target, the industrial structure must be adjusted and upgraded. Furthermore, it must start from a high-pollution and high-emission industry. Therefore, it is of practical significance to construct a low-carbon sustainability and green operation benefits of power generation enterprises to save energy and reduce emissions. In this paper, an intuitionistic fuzzy comprehensive analytic hierarchy process based on improved dynamic hesitation degree (D-IFAHP) and an improved extreme learning machine algorithm optimized by RBF kernel function (RELM) are proposed. Firstly, we construct the evaluation indicator system of low-carbon sustainability and green operation benefits of power generation enterprises. Moreover, during the non-dimensional processing, the evaluation index system is determined. Secondly, we apply the evaluation indicator system by an empirical analysis. It is proved that the D-IFAHP evaluation model proposed in this paper has higher accuracy performance. Finally, the RELM is applied to D-IFAHP to construct a combined evaluation model named D-IFAHP-RELM evaluation model. The D-IFAHP evaluation results are used as the input of the training sets of the RELM algorithm, which simplifies the comprehensive evaluation process and can be directly applied to similar projects.