Aerosol hygroscopicity is a key aerosol property, influencing a number of other physical properties, and the impacts of PM pollution on the environment, climate change, and health. The present work aims to provide insight into the contribution of major PM sources to aerosol hygroscopicity, focusing on an urban background site, with a significant impact from both primary and secondary sources. The EPA PMF 5.0 model was applied to PM2.5 chemical composition and hygroscopicity data collected from August 2016 to July 2017 in Athens, Greece. Source apportionment analysis resulted in six major sources, including four anthropogenic sources (vehicular exhaust and non-exhaust, heavy oil combustion, and a mixed source of secondary aerosol formation and biomass burning) and two natural sources (mineral dust and aged sea salt). The mixed source was found to be the main contributor to PM2.5 levels (44%), followed by heavy oil combustion (26%) and vehicular traffic exhaust and non-exhaust emissions (15%). The aerosol hygroscopic growth factor (GF) was found to be mainly associated with the mixed source (by 36%) and heavy oil combustion (by 24%) and, to a lesser extent, with vehicle exhaust (by 19%), aged sea salt (by 14%), and vehicle non-exhaust (by 6%).