This paper studies the characteristics of the heat waves that were observed in Athens, Greece since 1951. A heat wave is detected when two temperature criteria are fulfilled at the city centre: the daily maximum temperature value is at least 37 oC and the daily average temperature value is at least 31 oC. Information about the intensity, duration, timing in season and annual frequency of occurrence of heat waves were extracted. The slope of the linear fit of the annual number of heat wave days indicated that 1.30 more heat wave days per year were observed after 1992. The intensity and the duration of heat waves have also increased since 90s, while heat wave days have been detected during the whole summer since then, even during the first days of September. Additionally, air quality at the centre and at a suburb of Athens during the heat wave days that were identified during the last decade is examined. The daily average value of PM10 concentration exceeded 50 μg m-3 in 65% and 59% of the heat wave days at the urban and the suburban site, respectively, while the information and the alert O3 threshold were exceeded in 17% and 5% of the heat wave days, respectively, at the suburban site. The degradation of air quality during heat wave days is also verified by the means of the common air quality index. Moreover, it was found that O3 levels decrease when heat waves last more than 6 days.