In this study, coal samples with different moisture contents were prepared using a drying and humidification system. Coal samples were placed in a crucible and ignited using a heating wire, to which power was applied during coal combustion. The combustion radiance of coal samples with three moisture contents (0, 20, and 50%) was measured using a narrow-angle radiometer at three temperatures (10, 25, and 50 °C). A numerical simulation model was developed to predict the unsteady radiation characteristics of a coal layer burning on one-dimensional planar plates. The unsteady energy balance equation and radiative transfer equation were solved using the semi-implicit Runge-Kutta method and discrete ordinates method. In addition, the effect of dew condensation on the radiance was investigated. The greatest reduction in radiance was observed during the burning of the high-moisture coal. Furthermore, the effect of ash (converted from coal) on radiance was examined. The results demonstrated that certain changes in the optical properties during the burning of coal to ash can alter the absorption as well as anisotropic scattering, and thereby the radiance, as combustion proceeds.