To achieve higher energy security and lower emission of greenhouse gases (GHGs) and pollutants, the development of renewable energy has attracted much attention in Taiwan. In addition to its contribution to the enhancement of reliable indigenous resources, the introduction of renewable energy such as photovoltaic (PV) and wind power systems reduces the emission of GHGs and air pollutants by substituting a part of the carbon- and pollutant-intensive power with power generated by methods that are cleaner and less carbon-intensive. To evaluate the reduction potentials, consequential changes in the operation of different types of existing power plants have to be taken into account. In this study, a linear mathematical programming model is constructed to simulate a power mix for a given power demand in a power market sharing a cost-minimization objective. By applying the model, the emission reduction potentials of capacity extension case studies, including the enhancement of PV and wind power introduction at different scales, were assessed. In particular, the consequences of power mix changes in carbon dioxide, nitrogen oxides, sulfur oxides, and particulates were discussed. Seasonally varying power demand levels, solar irradiation, and wind strength were taken into account. In this study, we have found that the synergetic reduction of carbon dioxide emission induced by PV and wind power introduction occurs under a certain level of additional installed capacity. Investigation of a greater variety of case studies on scenario development with emerging power sources becomes possible by applying the model developed in this study.