The detection of polycyclic aromatic hydrocarbons (PAHs) by electrospray ionization (ESI) without additional reagents or targeted setup changes to the ionization source was observed in ultrafine particle (UFP) extracts, with high organic carbon (OC) concentrations, generated by a combustion aerosol standard (CAST) soot generator. Particulate matter (PM) was collected on filters, extracted with methanol, and analyzed by ESI Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Next to oxygen-containing species, pure hydrocarbons were found to be one of the most abundant compound classes, detected as [M + Na]+ or [M + H]+ in ESI+ and mostly as [M - H]- in ESI-. The assigned hydrocarbon elemental compositions are identified as PAHs due to their high aromaticity index (AI > 0.67) and were additionally confirmed by MS/MS experiments as well as laser desorption ionization (LDI). Thus, despite the relatively low polarity, PAHs have to be considered in the molecular attribution of these model aerosols and/or fresh emissions with low salt content investigated by ESI.