To understand the traffic emissions with high temporal and spatial resolutions on road, a mobile laboratory was developed. The objective of this study is to characterize on-road air pollution on Naebu express way surrounding the northern area of Seoul, Korea. We measured the number concentration of ultrafine particles larger than 5 nm and particle size distribution using a condensation particle counter and a fast mobility particle sizer, respectively on 3, 7, and 8 December 2009. The average ultrafine particle number concentration on the Naebu express way excluding tunnels was 126,000 particles/$cm^3$ and 4.2 times higher than that on internal road at Korea Institute of Science and Technology in Seoul, and more than twice higher than that measured on and at the arterial roads of Seoul in previous studies. The maximum ultrafine particle number concentration was observed at the tunnel sections. It was 232,000 particles/$cm^3$ and 1.8 times higher than average ultrafine particle number concentration for the other sections on Naebu express way. The ultrafine particle number concentration on the wider roads with higher traffic volume along the Han River was similar to that in the residential section, probably because of enhanced dilution effect in widely open environment. The size distribution of particles on the Naebu express way was highly fluctuated for a short duration. Ultrafine particles measured at the tunnel showed a bimodal size distribution with mode diameters of ~10 nm and ~50 nm. At the Han riverside section, ~10 nm particles appeared significantly compared with size distribution at the tunnel. This on-road measurement approach can be utilized to manage vehicle-related air pollution in urban area.