In indoor thermal analyses, the effect of humid air as a radiatively participating medium that absorbs and emits energy is often neglected. This simplification can underestimate important values in the results. This study presents a numerical investigation of the humid air that participates radiatively in the conjugate heat and mass transfer convection into a room modeled as a two-dimensional square cavity with a semitransparent wall (glass). The governing equations for mass, momentum, energy, species transport, turbulence, and radiative heat transfer were solved using the Finite Volume Method and coupled with the SIMPLEC algorithm. Two scenarios were analyzed: a radiatively participating medium (RPM) and a non-participating medium (NPM), under two climatic conditions (hot and cold). Results show that considering the radiatively participating medium breaks the symmetric patterns observed in the case of NPM. The energy absorbed by humid air enhances turbulent viscosity, buoyant forces, and indoor temperature. Humid air absorbs approximately 30–32% of the incident energy entering the enclosure. Finally, a correlation for the average temperature is proposed. The results provide insight into the influence of radiatively participating humid air on indoor-like thermal behavior. The study focuses on the analysis of fundamental transport mechanisms.