In this study, an optimization model was established based on the generalized contrastive weighted comprehensive scale index method. This model gives the evaluation indicators of SO2, NOx, CO, and TSP. It also innovatively introduces gas, the most harmful substance in underground coal mines, into the evaluation indicators. Moreover, the obvious hazardous concentration limit is used as the third standard concentration of the model. The scale sub-indices and the weights of SO2, NOx, CO, TSP, and gas are calculated, leading to the comprehensive scale index. Finally, the classification standard of the underground air quality is determined. An underground excavation face in Shaanxi Province is used as an example for air quality assessment. The air quality is generally poor at the points close to the working face, while that at the points far away from the working face is generally better. Furthermore, air quality optimization measures are given for areas with poor air quality.