In-vehicle air pollution has become a public health priority worldwide, especially for volatile organic compounds (VOCs) emitted from the vehicle interiors. Although existing literature shows VOCs emission is temperature-dependent, the impact of solar radiation on VOCs distribution in enclosed cabin space is not well understood. Here we made an early effort to investigate the VOCs levels in vehicle microenvironments using numerical modeling. We evaluated the model performance using a number of turbulence and radiation model combinations to predict heat transfer coupled with natural convection, heat conduction and radiation with a laboratory airship. The Shear–Stress Transport (SST) k-ω model, Surface-to-surface (S2S) model and solar load model were employed to investigate the thermal environment of a closed automobile cabin under solar radiation in the summer. A VOCs emission model was employed to simulate the spatial distribution of VOCs. Our finding shows that solar radiation plays a critical role in determining the temperature distribution in the cabin, which can increase by 30 °C for directly exposed cabin surfaces and 10 °C for shaded ones, respectively. Ignoring the thermal radiation reduced the accuracy of temperature and airflow prediction. Due to the strong temperature dependence, the hotter interiors such as the dashboard and rear board released more VOCs per unit time and area. A VOC plume rose from the interior sources as a result of the thermal buoyancy flow. A total of 19 mg of VOCs was released from the interiors within two simulated hours from 10:00 am to noon. The findings, such as modeled spatial distributions of VOCs, provide a key reference to automakers, who are paying increasing attention to cabin environment and the health of drivers and passengers.