The present study addresses the interaction effect of participating media radiation with the onset of double-diffusive convection in a square enclosure. Vertical walls are imposed with constant temperature and concentration, and the horizontal walls are impermeable and adiabatic. The boundaries of the enclosure are diffuse-gray, and the enclosed fluid isotropically scatters, emits, and absorbs thermal radiation. Numerical simulations have been performed for both aiding and opposing buoyancy conditions. The buoyancy ratio has been varied to simulate the effect of buoyancy driven flow and compositionally driven flow, along with transition of flow between the above. Optical properties like opacity of medium, scattering albedo, Planck number, and wall emissivity have been varied to depict their influence on flow and heat transfer. The modified MAC method is used for the solution of convective transport equations. Gradient dependent consistent hybrid upwind scheme of second order ( GDCHUSSO) is used for the discretization of the convective terms. The discrete ordinate method, with S8 approximation, is used to solve the radiative transport equation. The parametric results are provided in graphical and tabular form. Flow lines, isotherms, and isoconcentration contour maps are provided to bring clarity in the understanding of the momentum, heat, and solute transport phenomenon. The stabilization effect of thermal radiation at critical buoyancy ratio for buoyancy opposed flow is observed. © 2013 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library (). DOI 10.1002/htj.21108 [ABSTRACT FROM AUTHOR]