Traffic is considered one of the major polluting sectors and as a consequence a significant cause for the measured exceedances of ambient air quality limit values mainly in urban areas. The Greater Athens Area (located in Attica), the most populated area in Greece, faces severe air pollution problems due to the combination of high road traffic emissions, complex topography and local meteorological conditions. Even though several efforts were made to construct traffic emission inventories for Greece and Attica, still there is not a spatially and temporally resolved one, based on data from relevant authorities and organisations. The present work aims to estimate road emissions in Greece and Attica based on the top down approach. The programme COPERT 4 was used to calculate the annual total emissions from the road transport sector for the period 2006-2010 and an emission inventory for Greece and Attica was developed with high spatial (6 × 6 km(2) for Greece and 2 × 2 km(2) for Attica) and temporal (1-hour) resolutions. The results revealed that about 40% of national CO₂, CO, VOC and NMVOC values and 30% of NOx and particles are emitted in Attica. The fuel consumption and the subsequent reduction of annual mileage driven in combination with the import of new engine anti-pollution technologies affected CO₂, CO, VOC and NMVOC emissions. The major part of CO (56.53%) and CO₂ (66.15%) emissions was due to passenger cars (2010), while heavy duty vehicles (HDVs) were connected with NOx, PM₂.₅ and PM₁₀ emissions with 51.27%, 43.97% and 38.13% respectively (2010). The fleet composition, the penetration of diesel fuelled cars, the increase of urban average speed and the fleet renewal are among the most effective parameters towards the emission reduction strategies.