Vehicle emissions are identified as a major source of air pollution in metropolitan areas. Emission control programs in many cities have been implemented as part of larger scale transport policy interventions to control traffic pollutants and reduce public health risks. These interventions include provision of traffic-free and low emission zones and congestion charging. Various studies have investigated the impact of urban street configurations, such as street canyon in urban centers, on pollutants dispersion and roadside air quality. However, there are few investigations in the literature to study the impact of change of fleet composition and street canyon effects on the on-road pollutants concentrations and associated roadside pedestrian exposure to the pollutants. This study presents an experimental investigation on the traffic related gas and particle pollutants in and near major streets in one of the most developed business districts in Hong Kong, known as Central. Both street canyon and open roadway configurations were included in the study design. Mobile measurement techniques were deployed to monitor both on-road and roadside pollutants concentrations at different times of the day and on different days of a week. Multiple traffic counting points were also established to concurrently collect data on traffic volume and fleet composition on individual streets. Street canyon effects were evident with elevated on-road pollutants concentrations. Diesel vehicles were found to be associated with observed pollutant levels. Roadside black carbon concentrations were found to correlate with their on-road levels but with reduced concentrations. However, ultrafine particles showed very high concentrations in roadside environment with almost unity of roadside/on-road ratios possibly due to the accumulation of primary emissions and secondary PM formation. The results from the study provide useful information for the effective urban transport design and bus route reorganization to minimize the impact of traffic emissions on the urban air quality and public health. Observations on the elevated ultrafine particle concentrations in roadside pedestrian levels also demonstrate the urgent need to improve roadside air quality to reduce pedestrians’ health risks especially inside street canyon.