When a fire takes place in a tunnel, the surface of the asphalt pavement will burn and release a large amount of smoke, which is toxic to human health. Thus, in order to prevent the combustion of the asphalt pavement under fire, it is necessary to propose some methods to retard its physical and chemical reaction under the high temperature. In this study, ten different combinations of fire retardants and a control case where no fire retardant was applied were prepared for evaluation. The thermogravimetric (TG)–mass spectrometry (MS) tests were used to evaluate their effect on the fire retardance from mass and energy perspectives and the Fire Dynamics Simulator (FDS) software was used to evaluate the fire retardance from temperature and smoke distribution perspectives. In experimental analysis, the TG (thermogravimetric) and DTG (differential thermogravimetric) curves were used to analyze the mass loss rate and residual mass of the asphalt and the activation energy was calculated and analyzed as well. In addition, decay rate of mass loss rate and increasing rate of activation energy were proposed to evaluate the ease of combustion of the asphalt with and without fire retardants. The results show that in laboratory experiments, the fire retardant combination which includes 48% aluminum hydroxide, 32% magnesium hydroxide, 5% expanded graphite, and 15% encapsulated red phosphorous would lead to an improved effect of fire retardance. In numerical modeling, the temperature and smoke height distribution over time were adopted to evaluate the fire retardance effect. The temperature distribution was found to be symmetrical on both sides of the combustion point and the same combination as proposed in experimental analysis was found to have the best effect on fire retardance due to the largest decrease in temperature. Additionally, because of the highest smoke height distribution, an improved effect on smoke suppression was also found when this combination was applied.