The European decarbonization goals and requirement for energy independence are mostly relying on intermittent renewable energy sources for electrification. A numerical model was developed to simulate the operation of a steam generator, allowing a study of the potential impacts of retrofitting existing coal-fired power plants to operate with biomass or coal–biomass mixtures on combustion parameters and CO₂ emissions. The results obtained using the operational parameters of the Sines power plant indicate that a mixture of 25% coal and 75% pine sawdust allow operation at λ = 1.8, demonstrating that a small amount of coal allows operation near the coal combustion parameters (λ = 1.9). These conditions have the drawback of a reduction of 8.7% in adiabatic flame temperature but a significant reduction of 57.5% in CO₂ emissions, considering the biomass as carbon-neutral.