Assessing air quality in urban areas is vital for protecting public health, and low-cost sensor networks help quantify the population’s exposure to harmful pollutants effectively. This paper introduces an innovative method to calibrate air-quality sensor networks by combining CFD modeling with dependable AQ measurements. The developed CFD model is used to simulate traffic-related PM10 dispersion in a 1.6 × 2 km2 urban area. Hourly simulations are conducted, and the resulting concentrations are cross-validated against high-quality measurements. By offering detailed 3D information at a micro-scale, the CFD model enables the creation of concentration maps at sensor locations. Through regression analysis, relationships between low-cost sensor (LCS) readings and modeled outcomes are established and used for network calibration. The study demonstrates the methodology’s capability to provide aid to low-cost devices during a representative 24 h period. The precision of a CFD model can also guide optimal sensor placement based on prevailing meteorological and emission scenarios and refine existing networks for more accurate urban air quality representation. The usage of cost-effective air quality networks, high-quality monitoring stations, and high-resolution air quality modeling combines the strengths of both top-down and bottom-up approaches for air quality assessment. Therefore, the work demonstrated plays a significant role in providing reliable pollutant monitoring and supporting the assessment of environmental policies, aiming to address health issues related to urban air pollution.