For the radiative transfer problem in irregular three-dimensional non-gray absorbing media, the hybrid finite volume/finite element method was adopted to solve it. The calculating process of the hybrid method was deduced in orthogonal coordinates. Combining the theory of vector and matrix, the finite element equation general composition method coupling boundary condition was given. The radiative transfer of the attitude thruster nozzle expending segment and its interior absorbing media were regarded as the object to be solved. The spectral radiative luminance and 3~5 μm band radiative heat flux at the nozzle exiting section were obtained by adopting the method. Compared with the calculating results of the finite volume method, while the discrete value of the space or the angle is increased, the same point source spectral radiative luminance obtained by the two methods will get more and more closely. It is shown that the radiative transfer in irregular three-dimensional non-gray absorbing media can be solved by the hybrid finite volume/finite element method accurately.