The research investigated the absorption/adsorption efficiency of sulfur dioxide (SO2), heavy metals, and polycyclic aromatic hydrocarbons (PAHs) with different Ca-based sorbents in a spray dryer during incineration process. For further improving the adsorption capacity of Ca-based sorbents, different spraying pressure and additives were carried out in this study. Experimental results showed that CaO could be used as an alternative sorbent in the spray dryer at an optimal initial particle size distribution of spraying droplet. In the spray dryer, Ca-based sorbents provided a lot of sites for heavy metals and PAHs condensing and calcium and alkalinity to react with metals to form merged species. As a result, heavy metals and PAHs could be removed from the flue gas simultaneously by condensation and adsorption. The additions of additives NaHCO3, SiO2, and KMnO4 were also found to be effective in improving the removal efficiency of these air pollutants.