Long-term hour-specific air pollution exposure estimates have rarely been of interest in epidemiological research. However, this can be relevant for studies that aim to estimate the residential exposure for the hours that subjects mostly spend time there, or for those hours that they may work in another location. Here, we developed a model by spatially predicting the long-term diurnal curves of nitrogen dioxide (NO2) in Tehran, Iran, one of the most polluted and populated megacities in the Middle East. We used the statistical framework of functional data analysis (FDA) including ordinary kriging for functional data (OKFD) and functional analysis of variance (fANOVA) for modeling. The long-term NO2 diurnal curves had two distinct maxima and minima. The absolute minimum value of the city average was 40.6 ppb (around 4:00 p.m.) and the absolute maximum value was 52.0 ppb (around 10:00 p.m.). The OKFD showed the concentrations, the diurnal maximum/minimum values, and their corresponding occurring times varied across the city. The fANOVA highlighted that the effect of population density on the NO2 concentrations is not constant and depends on time within the diurnal period. The provided estimation of long-term hour-specific maps can inform future epidemiological studies to use the long-term mean for specific hour(s) of the day. Moreover, the demonstrated FDA framework can be used as a set of flexible statistical methods.