Charging in flames significantly affects the properties of the resultant particles produced because of its influence in almost all stages of particle formation. The charging characteristics of flame-generated sub 3 nm particles were investigated with three enhanced particle detectors including a high resolution differential mobility analyzer (DMA) coupled with an electrometer, a particle size magnifier coupled with a butanol-based condensation particle counter (PSM-bCPC), and an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF). Up to 95% of the flame-generated sub-3 nm particles were charged at a sampling height of 5 mm above the burner, indicating the existence of a strong ionization process in the investigated flame. This high fraction of charged particles contradicts the classical charging theories, which predict <1% charge fraction for particles below 3 nm. Positively and negatively charged sub-3 nm particles generated from a blank flame were dominated by organic ions and nitrate ions respectively. The flame-generated ions play an important role during titanium dioxide (TiO2) nanoparticle synthesis, as shown by the attachment of nitrate species on Ti-containing particles observed by the APi-TOF. The effects of the sampling height and precursor feed rate were also investigated. (C) 2016 The Combustion Institute. Published by Elsevier Inc. All rights reserved.