Urban air pollution caused by light-duty passenger vehicles poses critical environmental and public health challenges in megacities like Tehran. In this study, we dynamically estimated vehicular emissions by collecting second-by-second speed and acceleration data from 16 representative routes, including 2 residential, 8 urban, and 6 highway segments, across metropolitan Tehran. We integrated the Vehicle Specific Power (VSP) method with the International Vehicle Emissions (IVE) model to assess real-time emission patterns across four time intervals (08:00, 12:00, 16:00, and 23:00). Our measurements showed that average speeds ranged from 14.0 to 25.97 km/h in residential areas, 10.62 to 42.13 km/h in urban corridors, and 16.43 to 67.15 km/h on highways. We found that VSP values predominantly fell within bins 8–14, reflecting acceleration-intensive and stop-and-go traffic during peak hours. We estimated emissions per kilometer as follows: CO (0.47–0.57 g), NOₓ (0.11–0.23 g), CO₂ (240.7–411.5 g), VOC (0.13–0.19 g), and NMVOC (0.12–0.18 g). During peak hours, emissions increased by 40–50% compared to off-peak periods, correlating with VSP clustering around bins 8–10, while smoother traffic conditions (VSP ≥12) during off-peak hours reduced emissions. This study is among the first in the region to combine second-by-second VSP profiles with the IVE model to produce high-resolution, time-resolved urban emission estimates. Our findings highlight how dynamic traffic modeling can help policymakers design smart traffic signal systems, manage congestion, and improve air quality policies tailored to real-time conditions in megacities.