This paper presents experimental results from a typical school building in Athens, equipped partly with a green roof system (GRS). Environmental monitoring took place in six classrooms located both under the concrete roof and the GRS sectors as well as in the immediate external environment during the warm and cold periods of a school year. Daily measurements of pollutants CO 2 , TVOCs (Total Volatile Organic Compound), PM 1 , PM 2.5 , and PM 10 were performed in selected classes. Moreover, indoor ambient temperature (T) and relative humidity (RH) measurements were implemented in order to estimate the absolute humidity (AH) and assess the indoor environmental conditions. The results highlight that during summer, the GRS reduces temperature in a classroom on the top floor by about 2.8 • C, in comparison with the respective classroom under the concrete roof and that AH remained relatively stable for both classrooms. Amid winter, a reverse behavior occurs only for temperature. Moreover, air exchange rates (AER) were calculated by using the CO 2 decay method for all of the classrooms. The results demonstrated insufficient ventilation for all experimental sights. Finally, concentrations of PM 1 , PM 2.5 and PM 10 , were found to be relatively decreased, with average values of 0.79, 3.39, and 27.80 µg m −3 . Levels of CO 2 and TVOCs were elevated during class hours ranging from 469 to 779 ppm and from 6.63 ppm to 13.33 ppm, respectively, but generally within the respective limits of exposure. The examination of the indoor/outdoor (I/O) ratio of air pollutants, demonstrated that the outdoor meteorology affects only PM 1 and PM 2.5 , as PM 10 and TVOCs are strongly affected by internal sources and the activities of pupils.