The aim of the present study is to investigate the variability of the tropospheric ozone and nitrogen dioxide (NO2) columns over mainland Greece, by using observations carried out by satellite-borne instrumentation and Multi Sensor Reanalysis. The results obtained show that the tropospheric ozone residual (TOR) dispersed farther away than the tropospheric NO2 column (TNO), due to the longer TOR's lifetime in respect to that of TNO. This results in the influence of the air quality of the nearby southern islands from the air pollution of the greater Athens basin. Furthermore, the TOR and TNO columns over Athens, for the period October 2004 to December 2011 were found to be negatively correlated with a correlation coefficient -0.85, in contrast to recent findings which suggested strong positive correlation. Interestingly, this strong negative correlation into a slight positive correlation when the TNO concentration becomes higher than around 4 × 1015 molec cm-2, thus being best fitted by a quadratic relationship. In addition, the temporal evolution of TOR during 1979-1993 showed a decline of 0.2% per decade and just after 1993 it seems to obey a positive trend of 0.1% per decade, thus recovering during the period 1993-2011 almost 63% of the lost TOR amounts through the years 1979-1993. Finally, the association between TOR, the total ozone column (TOZ), the tropopause height and the outgoing longwave radiation (OLR) is presented by analysing observations during 1979-2011. An unexpected positive correlation between OLR and TOR was found, which may probably be attributed to the fact that enhanced abundance in tropospheric water vapor reduces the summertime TOR maximum by destructing ozone in the lower and middle troposphere through uptake mechanisms, thus emitting higher amounts of longwave radiation upwards.