This paper presents the comparative results obtained from X-ray and neutron pair distribution function (PDF) analysis aimed at determining the variability in aluminosilicate glass chemistry in five types of class F fly ash (FA). Results have been discussed in light of the complementary information provided by the two methods in order to give a comprehensive overview of FA structure at the nanoscale. The analysis of short range correlations reveals that the bulk glassy structure of FA sources differing in chemical composition are relatively similar, but some specific distinctions in atomic structure are visible in those containing high levels of amorphous VI-coordinated aluminum (e.g., amorphous mullite/alumina), iron and/or carbon (with similar local bonding environment to graphite). The obtained experimental results fill a deficit in literature in the atomic structure and associated variability for class F FA, which is extensively used in several industrial applications including as raw material in alkali-activated cements. (C) 2016 Elsevier Ltd. All rights reserved.