Atmospheric pollution has recently drawn significant attention due to its proven adverse effects on public health and the environment. This concern has been aggravated specifically in Southeast Asia due to increasing vehicular use, industrial activity, and agricultural burning practices. Consequently, elevated PM2.5 concentrations have become a matter of intervention for national authorities who have addressed the needs of monitoring air pollution by operating ground stations. However, their spatial coverage is limited and the installation and maintenance are costly. Therefore, alternative approaches are necessary at national and regional scales. In the current paper, we investigated interpolation models to fuse PM2.5 measurements from ground stations and satellite data in an attempt to produce spatially continuous maps of PM2.5 nationwide over Thailand. Four approaches are compared, namely the inverse distance weighted (IDW), ordinary kriging (OK), random forest (RF), and random forest combined with OK (RFK) leveraging on the NO2, SO2, CO, HCHO, AI, and O3 products from the Sentinel-5P satellite, regulatory-grade ground PM2.5 measurements, and topographic parameters. The results suggest that RFK is the most robust, especially when the pollution levels are moderate or extreme, achieving an RMSE value of 7.11 μg/m3 and an R2 value of 0.77 during a 10-day long period in February, and an RMSE of 10.77 μg/m3 and R2 and 0.91 during the entire month of March. The proposed approach can be adopted operationally and expanded by leveraging regulatory-grade stations, low-cost sensors, as well as upcoming satellite missions such as the GEMS and the Sentinel-5.