Studies of health effects of air pollution exposure are limited by inability to accurately determine dose and exposure of air pollution in field trials. We explored the feasibility of using a mobile selected ion flow tube mass spectrometry (SIFT-MS) device, housed in a van, to determine ambient air and breath levels of benzene, xylene and toluene following exercise in areas of high motor vehicle traffic. The breath toluene, xylene and benzene concentration of healthy subjects were measured before and after exercising close to a busy road. The concentration of the volatile organic compounds (VOCs), in ambient air were also analysed in real time. Exercise close to traffic pollution is associated with a two-fold increase in breath VOCs (benzene, xylene and toluene) with levels returning to baseline within 20 min. This effect is not seen when exercising away from traffic pollution sources. Situating the testing device 50 m from the road reduced any confounding due to VOCs in the inspired air prior to the breath testing manoeuvre itself. Real-time field testing for air pollution exposure is possible using a mobile SIFT-MS device. This device is suitable for exploring exposure and dose relationships in a number of large scale field test scenarios.