In this paper a new methodology is presented by the authors for the numerical treatment of radiative heat transfer in emitting, absorbing and scattering media. This methodology is based on the utilisation of Control Volume Finite Element Method (CVFEM) and the use, for the first time, of matrix formulation of the discretized Radiative Transfer Equation (RTE). The advantages of the proposed methodology is to avoid problems that confronted when previous techniques are used to predict radiative heat transfer, essentially, in complex geometries and when there is scattering and/or non-black boundaries surfaces. Besides, the new formulation of the discretized RTE presented in this paper makes it possible to solve the algebraic system by direct or iterative numerical methods. The theoretical background of CVFEM and matrix formulation is presented in the text. The proposed technique is applied to different test problems, and the results compared favourably against other published works. Moreover this paper discusses in detail the effects of some radiative parameters, such as optical thickness and walls emissivities on the spatial evolution of the radiant heat flux. The numerical simulation of radiative heat transfer for different cases using the algorithm proposed in this work has shown that the developed computer procedure needs an accurate CPU time and is exempt of any numerical oscillations.