Contact-angle measurements and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize polypropylene (PP) films that were exposed to laminar premixed air:natural gas flames containing small quantities of nitrous oxide. During combustion, the nitrous oxide generates gas-phase nitrogen oxides that lead to the affixation of nitrogen-containing functional groups to the PP surfaces. Treatment of PP in nitrous oxide-containing flames also leads to an increase in surface oxidation and markedly improves wettability when compared with standard flame treatments. The chemical form of the nitrogen affixed to the PP surface is strongly dependent on the flame equivalence ratio. Fuel-lean flames tend to affix highly oxidized forms of nitrogen such as nitrate and nitro groups, while fuel-rich flames tend to affix less-oxidized nitrogen groups such as nitroso, oxime, amide, and amine. A computational model, SPIN, was used to elucidate the chemistry of the flame as it impinges upon the cooled PP surface, The SPIN modeling indicates that the principal reactive gas-phase species at or near the PP surface are O-2, OH, Ii, NO, NO2, HNO, and N2O. A number of possible reactions between these species and the PP van account for the formation of the various nitrogen functional groups observed.