A vector radiative transfer numerical model of the coupled ocean-atmosphere system is developed based on the matrix-operator method, which is named PCOART. Using the Fourier analysis, the vector radiative transfer equation (VRTE) is separated into a set of equations depending only on the observation zenith angle. Using the Gaussian-Quadrature method, VRTE is finally transferred into the matrix equation solved by the adding-doubling method. According to the reflective and refractive properties of the ocean-atmosphere interface, the vector radiative transfer numerical model of the ocean and atmosphere is coupled in PCOART. Compared with the exact Rayleigh scattering look-up tables of MODIS (Moderate-resolution Imaging Spectroradiometer), it is shown that PCOART is an exactly numerical model, and the processing methods of the multi-scattering and polarization are correct. Also, validated with the standard problems of the radiative transfer in water, it is shown that PCOART can be used to calculate the underwater radiative transfer problems. Therefore, PCOART is a useful tool for exactly calculating 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.