In this paper, measurements of benzene, toluene, p,m-xylene, ozone (O3), nitrogen dioxide (NO2), and sulfur dioxide (SO2) made using the differential optical absorption spectroscopy (DOAS) technique during a 4-month period of summer 2000 (June-September) in Athens, Greece, are presented. An assessment of benzene mean value concentrations during this 4-month period exceeded 10 microg/m3, which is 2 times greater than the average yearly limit proposed by European authorities. Toluene measurements present mean values of approximately 33 microg/m3. Benzene and especially toluene measurements are highly correlated with NO2 and anticorrelated with O3. High values of benzene, NO2, and toluene are also correlated with winds from the southeast section, an area of industrial activity where emissions of volatile organic compounds (VOCs) have been recorded in previous studies. O3 is correlated with winds from the south-southwest section affected by the sea breeze circulation. Diurnal variations of O3, NO2, and SO2 concentrations are compatible with measurements from the stations of the Ministry of Environment's network. Outliers are combined with weak winds from the south-southwest. As far as p,m-xylene measurements are concerned, there is a poor correlation between gas chromatography (GC) and DOAS Opsis measurements, also observed in previous relevant campaigns and eventually a criticism in the use of the DOAS Opsis model for the measurement of p,m-xylene.