The increasing quantity of air pollutants generated by automobiles can cause significant harm in relatively enclosed indoor environments. Studying the distribution of pollutants under different conditions in underground parking garages is of great significance for improving indoor air quality and reducing casualties in the event of a fire. This article presents a geometric model of an underground parking garage based on PHOENICS modeling. The related results of CO concentration distribution and fire temperature distribution under ventilation and fire conditions are obtained. Based on the CO concentration and velocity distribution as well as the temperature distribution during a fire, reasonable suggestions are proposed to improve indoor air quality and reduce casualty rates in fire incidents. The results show that under ventilation conditions, adjusting the position of the induced ventilation fan can maintain CO concentrations below 30 ppm in partitions one to three and below 37 ppm in partitions four to six. The temperature of smoke gases remained below 50 °C during the evacuation time, and only a small area exhibited CO levels exceeding 2000 ppm. The existing ventilation exhaust system provides effective fire protection, as it minimally affects personnel evacuation due to the relatively lower smoke temperature.