Peroxyacetilnitrates (PAN) is the most characteristic photoxidant of a range of secondary pollutants formed by the photochemical reaction of hydrocarbons with nitrogen oxides in the atmosphere: it is phytotoxic and shows an increasing role in human health effects due to ambient air exposure, especially in presence of high ozone concentrations. Because of the similarity of the conditions required for their photochemical production PAN is observed in conjunction with elevated ozone concentrations. PAN has very low natural background concentrations so it is the very specific indicator of anthropogenic photochemical air pollution. In this paper we report PAN concentrations determined in Rome urban area during winter- and summer-period. PAN measurements were carried out by means of a gas-chromatograph equipped with an Electron Capture Detector (ECD) detector. For identifying the acute episodes of atmospheric photochemical pollutants the relationship between PAN and the variable Ox (=NO2+O3) which describes the oxidation process evolution is investigated. The role of Volatile Organic Compounds and PAN in the ozone formation is investigated as well the issue of taking in account the autovehicular emissions for checking the NOx fraction in fuel.