The numerical model of the vector radiative transfer of the coupled ocean-atmosphere system is developed based on the matrix-operator method, which is named PCOART. In PCOART, using the Fourier analysis, the vector radiative transfer equation (VRTE) splits up into a set of independent equations with zenith angle as only angular coordinate. Using the Gaussian-Quadrature method, VRTE is finally transferred into the matrix equation, which is calculated by using the adding-doubling method. According to the reflective and refractive properties of the ocean-atmosphere interface, the vector radiative transfer numerical model of ocean and atmosphere is coupled in PCOART. By comparing with the exact Rayleigh scattering look-up-table of MODIS(Moderate-resolution Imaging Spectroradiometer), it is shown that PCOART is an exact numerical calculation model, and the processing methods of the multi-scattering and polarization are correct in PCOART. Also, by validating with the standard problems of the radiative transfer in water, it is shown that PCOART could be used to calculate the underwater radiative transfer problems. Therefore, PCOART is a useful tool to exactly calculate the vector radiative transfer of the coupled ocean-atmosphere system, which can be used to study the polarization properties of the radiance in the whole ocean-atmosphere system and the remote sensing of the atmosphere and ocean.