Modern automotive gasoline engines have highly efficient after-treatment systems that reduce exhaust gas emissions. However, this efficiency greatly depends on the conditions of the exhaust gas, mainly the temperature and air−fuel ratio. The temperature instability during transient conditions may cause a reduction in the efficiency of the three-way catalyst (TWC). By using a thermal energy storage system before TWC, this negative effect can be suppressed. In this paper, the effects of the temperature stabilization on the efficiency of the three-way catalyst were investigated on a 1-D turbocharged gasoline engine model, with a focus on fuel consumption and emissions. The thermal energy storage system (TESS) was based on PCM materials and was built in the exhaust between the turbine and TWC to use the energy of the exhaust gas. Three different materials were picked up as possible mediums in the storage system. Based on the results, the usage of a TESS in a gasoline after-treatment system has shown great potential in improving TWC efficiency. This approach can assist the catalyst to operate under optimal conditions during the drive. In this study, it was found that facilitating the heat transfer between the PCM and the catalyst can significantly improve the emissions’ reduction performance by avoiding the catalyst to light out after the cold start. The TESS with PCM H430 proved to reduce the cumulative CO and HC emissions by 8.2% and 10.6%, respectively, during the drive. Although a TES system increases the after-treatment cost, it can result in emission reductions and fuel consumption over the vehicle’s operating life.