In the present study, we investigate the variation of NOx)(NO + NO2) and O3 concentrations and the relation between the extreme events (episodes) of NOx and O3 concentrations and the relevant meteorological conditions in the urban atmosphere of the Athens basin. Hourly data of NO, NO2 and O3 concentrations from 10 representative monitoring sites located in the Athens basin were used, covering the 10-year time period from 1994 to 2003. The results of our analysis show that the concentrations of air pollutants differ significantly from one monitoring site to another, due to the location and proximity of each station to the emission sources. For each site, there are also significant differences in NOx and O3 concentrations from day to day, as well as from month to month and/or from season to season. The annual and seasonal variations show higher NO values in winter and lower in summer. On the contrary, NO2 and O3 values are higher in summer (photochemical production of O3) and lower in winter. These differences are attributed, to a large extent, to the prevailing synoptic and meteorological conditions, the most important between them being the wind direction and speed as well as the atmospheric pressure. Our analysis of the identified 179 extreme NOx air pollution events shows that most of them took place under anticyclonic conditions, associated with calm or weak winds (speed <2.5 ms(-1)) of mostly southern to southwestern directions, as well as with low air temperatures and intense stable surface atmospheric conditions. There exists a significant decreasing tendency in NOx air pollution episodic events over the 10-year study period, resulting in very few to none events in the period from 2000 to 2003. As far as it concerns the extreme O3 concentrations, 34 air pollution events were identified, occurring under high air temperatures, variable weak winds and intense solar irradiation. The trends of O3 concentrations are stronger in suburban sites than in urban ones.