In this paper, the control volume finite element method (CVFEM) is coupled with the weighted sum of gray gases model (WSGGM) to study the radiative heat transfer in a nongray medium. To the best of our knowledge, the CVFEM–WSGGM is applied for the first time to simulate real-gas. The accuracy of the proposed method is tested through one- and two-dimensional radiative heat transfer within an enclosure filled with a single composition (water vapor or carbon dioxide) or a mixture of H2O, CO2, and N2. Compared to the discrete ordinates method (DOM)–statistical narrow band model (SNBM), the proposed method, using the WSGG model parameters due to Smith or Farag, yields much accurate results than the zonal method (ZM)–WSGGM and DOM–WSGGM. In addition, the present method needs very less control volumes and angles, and consequently computational time, compared to the DOM and ZM coupled with WSGGM.