The combustion of conventional fuels (Diesel and Jet A-1) with 10–20% vol. oxygenated biofuels (ethanol, 1-butanol, methyl octanoate, rapeseed oil methyl ester, diethyl carbonate, tri(propylene glycol)methyl ether, i.e., CH3(OC3H6)3OH, and 2,5-dimethylfuran) and a synthetic paraffinic kerosene was studied. The experiments were performed using an atmospheric pressure laboratory premixed flame and a four-cylinder four-stroke Diesel engine operating at 1500 rpm. Soot samples from kerosene blends were collected above a premixed flame for analysis. Polyaromatic hydrocarbons (PAHs) were extracted from the soot samples. After fractioning, they were analyzed by high-pressure liquid chromatography (HPLC) with UV and fluorescence detectors. C1 to C8 carbonyl compounds were collected at the Diesel engine exhaust on 2,4-dinitrophenylhydrazine coated cartridges (DNPH) and analyzed by HPLC with UV detection. The data indicated that blending conventional fuels with biofuels has a significant impact on the emission of both carbonyl compounds and PAHs adsorbed on soot. The global concentration of 18 PAHs (1-methyl-naphthalene, 2-methyl-naphthalene, and the 16 US priority EPA PAHs) on soot was considerably lowered using oxygenated fuels, except 2,5-dimethylfuran. Conversely, the total carbonyl emission increased by oxygenated biofuels blending. Among them, ethanol and 1-butanol were found to increase considerably the emissions of carbonyl compounds.