Concern is growing about the effects of urbanization on air pollution and health. Nitrogen dioxide (NO2) released primarily from combustion processes, such as traffic, is a short-lived atmospheric pollutant that serves as an air-quality indicator and is itself a health concern. We derive a global distribution of ground-level NO2 concentrations from tropospheric NO2 columns retrieved from the Ozone Monitoring Instrument (OMI). Local scaling factors from a three-dimensional chemistry-transport model (GEOS-Chem) are used to relate the OMI NO2 columns to ground-level concentrations. The OMI-derived surface NO2 data are significantly correlated (r = 0.69) with in situ surface measurements. We examine how the OMI-derived ground-level NO2 concentrations, OMI NO2 columns, and bottom-up NOx emission inventories relate to urban population. Emission hot spots, such as power plants, are excluded to focus on urban relationships. The correlation of surface NO2 with population is significant for the three countries and one continent examined here: United States (r = 0.71), Europe (r = 0.67), China (r = 0.69), and India (r = 0.59). Urban NO2 pollution, like other urban properties, is a power law scaling function of the population size: NO2 concentration increases proportional to population raised to an exponent. The value of the exponent varies by region from 0.36 for India to 0.66 for China, reflecting regional differences in industrial development and per capita emissions. It has been generally established that energy efficiency increases and, therefore, per capita NOx emissions decrease with urban population; here, we show how outdoor ambient NO2 concentrations depend upon urban population in different global regions.