This study reports emission of organic particulate matter by light-duty vehicles (LDVs) and heavy-duty vehicles (HDVs) in the city of São Paulo, Brazil, where vehicles run on three different fuel types: gasoline with 25 % ethanol (called gasohol, E25), hydrated ethanol (E100), and diesel (with 5 % biodiesel). The experiments were performed at two tunnels: Jânio Quadros (TJQ), where 99 % of the vehicles are LDVs, and RodoAnel Mário Covas (TRA), where up to 30 % of the fleet are HDVs. Fine particulate matter (PM_2.5) samples were collected on quartz filters in May and July 2011 at TJQ and TRA, respectively. The samples were analyzed by thermal-desorption proton-transfer-reaction mass spectrometry (TD-PTR-MS) and by thermal–optical transmittance (TOT). Emission factors (EFs) for organic aerosol (OA) and organic carbon (OC) were calculated for the HDV and the LDV fleet. We found that HDVs emitted more PM[subscript 2.5] than LDVs, with OC EFs of 108 and 523 mg kg^-1 burned fuel for LDVs and HDVs, respectively. More than 700 ions were identified by TD-PTR-MS and the EF profiles obtained from HDVs and LDVs exhibited distinct features. Unique organic tracers for gasoline, biodiesel, and tire wear have been tentatively identified. nitrogen-containing compounds contributed around 20 % to the EF values for both types of vehicles, possibly associated with incomplete fuel burning or fast secondary production. Additionally, 70 and 65 % of the emitted mass (i.e. the OA) originates from oxygenated compounds from LDVs and HDVs, respectively. This may be a consequence of the high oxygen content of the fuel. On the other hand, additional oxygenation may occur during fuel combustion. The high fractions of nitrogen- and oxygen-containing compounds show that chemical processing close to the engine / tailpipe region is an important factor influencing primary OA emission. The thermal-desorption analysis showed that HDVs emitted compounds with higher volatility, and with mainly oxygenated and longer chain hydrocarbons than LDVs.