A Chebyshev collocation spectral method (CSM) is presented to solve transient coupled radiative and conductive heat transfer in three-dimensional absorbing, emitting, and scattering medium in Cartesian coordinates. The walls of the enclosures are considered to be opaque, diffuse, and gray and have specified temperature boundary conditions. The CSM is adopted to solve both the radiative transfer equation (RTE) and energy conservation equation in spatial domain, and the discrete ordinates method (DOM) is used for angular discretization of RTE. The exponential convergence characteristic of the CSM for transient coupled radiative and conductive heat transfer is studied. The results using the CSM show very satisfactory calculations comparing with available results in the literature. Based on this method, the effects of various parameters, such as the scattering albedo, the conduction–radiation parameter, the wall emissivity, and the optical thickness, are analyzed.