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Ultraviolet photocatalytic oxidation (UV-PCO) is a promising gaseous volatile organic compounds (VOCs) elimination method, of which the PCO kinetics are closely related to the radiation and airflow (contaminants) fields. Mathematical models have been developed in extensive studies to demonstrate the PCO kinetic reactions. Computational fluid dynamics (CFD) simulation was also carried out to display the irradiance and flow fields in the reactor. However, it still lacks an in-depth understanding of the light and mass transfer within the porous film coating where the microscopic structures dominate. To close this gap, this paper concentrates on the development of mathematical models for describing the light propagation, mass transfer, and reaction kinetics within the porous film coating. Incorporated with a CFD model for solving the mass, momentum and energy conservation, the sophisticated PCO process in the reactor can be accurately reproduced. The developed models have been validated by the experimental data, and are comparable with other models in the literature. The developed numerical models provide the implications of mass transfer for film coating UV-PCO reactor design.