Monitoring was carried out of particulate concentrations whilst simultaneously walking and driving 48 routes in London, UK. Monitoring was undertaken during May and June 2005. Route lengths ranged from 601 to 1351 m, and most routes were travelled in both directions. Individual journey times ranged from 1.5 to 15 min by car (average 3.7 min) and 7.3 to 30 min (average 12.8 min) whilst walking; car trips were therefore repeated up to 5 times for each single walking trip and the results averaged for the route. Car trips were made with windows closed and the ventilation system on a moderate setting. Results show that mean exposures while walking are greatly in excess of those while driving, by a factor 4.7 for the coarse particle mass (PM10-PM2.5), 2.2 for the fine particle mass (PM2.5-PM1), 1.9 for the very fine particle mass (<PM1) and 1.4 for ultrafine particle number density. The reduced in-car exposures appear to occur largely because the filtration system helps to prevent ingress of particles, so that the vehicle acts as a more-or-less independent micro-environment, insulated against much of air pollution present in the street. When account is also taken of the additional travel time involved in walking, these excesses are further increased: to factors of 15.6, 7.4, 6.5 and 4.4, respectively. Individuals who change their travel mode from car to walking in response to policies aimed at encouraging a modal shift in travel behavior are thus likely to experience considerably increased journey-time personal exposures to traffic-related air pollution. More effort is consequently needed to increase separation between road vehicles and pedestrians if negative effects of these policies are to be avoided.