In order to reduce the relative error of carbon emission prediction and improve the prediction efficiency, a new prediction method of coal combustion carbon emission of power generation enterprises based on rough set and grey SVM is proposed in this paper. Firstly, according to the rough set theory, the carbon emission data of power generation enterprises are deeply mined to enrich the data sources of carbon emission prediction. Secondly, grey GM model and SVM model are constructed according to the mining results. Finally, combined with the grey GM model and SVM model, the prediction model of coal combustion carbon emission of power generation enterprises is constructed to complete the prediction of carbon emission. The experimental results show that compared with the traditional prediction methods, the prediction relative error of this method is significantly reduced, and the prediction time is significantly reduced.