Modeling approaches have been utilized to simulate ambient pollutant concentrations, but very limited efforts have been made to estimate volatile organic compounds in the atmosphere. For this reason, an hourly grid-scale simulation model was developed to determine ambient air concentrations of benzene, toluene, ethylbenzene, and xylene (BTEX). BTEX data were collected over a one-year time frame from the database of the Taiwan Environmental Protection Administration's photochemical assessment monitoring stations. Multivariate linear regression models were used along with correlation analysis to simulate hourly grid-scale BTEX concentrations, using criteria pollutants and selected meteorological variables as predictors. The simulation model was validated in the southern Taiwan area via a portable micro gas chromatography system (n = 121) with significant correlation (r = 0.566**, ** indicated p < 0.01). Moreover, the grid-scale model was applied to areas covering about 72% of the population in Taiwan. A geographic information system (GIS) was used to visualize the spatial distribution of BTEX concentrations from the modeling results. This new grid-scale modeling strategy, which incorporated the GIS output of the simulated data, provides a useful alternative tool for personal exposure analysis and health risk assessment of ambient air BTEX.