The increasing global demand for palm oil and its products has led to a significant growth in palm plantations and palm oil production. Unfortunately, these bring serious environmental problems, largely because of the large amounts of waste material produced, including palm kernel shell (PKS). In this study, we used computational fluid dynamics (CFD) to investigate the PKS co-firing of a 300 MWe pulverized coal-fired power plant in terms of thermal behavior of the plant and the CO2, CO, O2, NOx, and SOx produced. Five different PKS mass fractions were evaluated: 0%, 10%, 15%, 25%, and 50%. The results suggest that PKS co-firing is favorable in terms of both thermal behavior and exhaust gas emissions. A PKS mass fraction of 25% showed the best combustion characteristics in terms of temperature and the production of CO2, CO, and SOx. However, relatively large amounts of thermal NOx were produced by high temperature oxidation. Considering all these factors, PKS mass fractions of 10%–15% emerged as the most appropriate co-firing condition. The PKS supply capacity of the palm mills surrounding the power plants is a further parameter to be considered when setting the fuel mix.