Levels and sources of non-Methane Hydrocarbons (NMHCs) were investigated at the urban background Thissio station, close to the historical center of Athens (Greece) from March 2016 to February 2017 (12 months), by means of an automated GC-FID. Alkanes dominated over aromatics and alkenes, with hourly mean levels ranging from detection limit up to 60 μg m−3 for i-pentane and 90 μg m−3 for toluene. Higher levels were recorded in the cold period relative to the warmer one. In addition, NMHCs seasonal diurnal cycles were characterized by a bimodal pattern, following the trend of tracers of anthropogenic sources. The Positive Matrix Factorization (PMF) was used for the allocation of NMHC to their sources. Five factors were identified and quantified, with traffic-related sources being the main one contributing up to 60% to total NMHCs, while biomass burning contributes up to 19%. A supplementary PMF assimilation was applied on a seasonal basis further including α-pinene, C6-C16 alkanes and aromatics. This PMF resulted to a seven-factor solution that allowed the examination of two additional sources, in addition to five already identified, highlighting the main contribution of anthropogenic sources (70%) to α-pinene.