Traffic is a main source of air pollutants in urban areas and consequently daily peak exposures tend to occur during commuting. Personal exposure to particulate matter (PM) was monitored while cycling and travelling by bus, car and metro along an assigned route in Lisbon (Portugal), focusing on PM2.5 and PM10 (PM with aerodynamic diameter <2.5 and 10 µm, respectively) mass concentrations and their chemical composition. In vehicles, the indoor-outdoor interplay was also evaluated. The PM2.5 mean concentrations were 28 ± 5, 31 ± 9, 34 ± 9 and 38 ± 21 µg/m3 for bus, bicycle, car and metro modes, respectively. Black carbon concentrations when travelling by car were 1.4 to 2.0 times higher than in the other transport modes due to the closer proximity to exhaust emissions. There are marked differences in PM chemical composition depending on transport mode. In particular, Fe was the most abundant component of metro PM, derived from abrasion of rail-wheel-brake interfaces. Enhanced concentrations of Zn and Cu in cars and buses were related with brake and tyre wear particles, which can penetrate into the vehicles. In the motorised transport modes, Fe, Zn, Cu, Ni and K were correlated, evidencing their common traffic-related source. On average, the highest inhaled dose of PM2.5 was observed while cycling (55 µg), and the lowest in car travels (17 µg). Cyclists inhaled higher doses of PM2.5 due to both higher inhalation rates and longer journey times, with a clear enrichment in mineral elements. The presented results evidence the importance of considering the transport mode in exposure assessment studies.