Effects of three oxygenate additives (methanol, ethanol, and MTBE) on the formation of polycyclic aromatic hydrocarbons (PAHs) and soot in laminar, premixed, atmospheric pressure, fuel-rich flames of n-heptane were studied at an equivalence ratio of 2.10. A heated quartz microprobe coupled to online gas chromatography/mass spectrometry was used to establish the identities and absolute concentrations of major, minor, and trace species by the direct analysis of samples withdrawn from the flames. Benzene was the most abundant aromatic compound identified. The largest PAH detected was the family of C18H10 (molecular weight of 226) that includes cyclopenta[cd]pyrene and benzo[ghi]fluoranthene. Soot particle diameters, number densities, and volume fractions were determined using classical light scattering and extinction measurements. All the oxygenate additives studied reduced the mole fractions of aromatic and PAH species, as well as soot formation. However, the reduction in soot formation was comparable for different oxygenates under the experimental conditions investigated.