This work studied the influence of additive concentration on the analytical pyrolysis of tobacco powder at 500 degrees C. Additive mass concentration of 5, 10, and 20% ZnCl2 and 5, 10, and 20% MgCl2 were studied. The addition of ZnCl2 and MgCl2 to tobacco powder promoted the formation of vapors with higher contents of acetic acid and furfural and for both, the higher the concentration the lower the nicotine content. However, there were some losses related to bio-oil quality, such as higher contents of oxygenated compounds, ketones and aldehydes, and carboxylic acids. Results indicate that bio-oils with higher acetic acid and phenolics contents will be generated from tobacco residue with 5% MgCl2, and bio-oils with higher furfural contents will be produced from the residue with 20% MgCl2. The pyrolytic reaction of tobacco residue with 10% ZnCl2 would result in a fuel oil with ignition quality.