Atmospheric correction is the key step for satellite ocean color remote sensing. However, most of the existing atmospheric correction algorithms do not consider the effects of Earth curvature. In fact, Earth curvature has a significant impact on satellite observation signals under large solar zenith angles or large viewing zenith angles. In this study, based on the Monte Carlo method, a vector radiative transfer model with spherical shell atmosphere geometry (hereafter our SSA-MC model) considering the influence of Earth curvature was established, which can be applied to conditions with high solar zenith angles or high viewing zenith angles. Our SSA-MC model was first compared with the Adams&Kattawar model, and the results show that the mean relative differences are 1.72%, 1.36% and 1.28% for solar zenith angles of 0 ∘, 70.47 ∘ and 84.26 ∘, respectively. Moreover, our SSA-MC model was further validated by more recently benchmarks from Korkin's scalar and vector models, and the results show that the relative differences are mostly less than 0.5% even at extremely high solar zenith angles (84.26 ∘). Then, our SSA-MC model was verified with the Rayleigh scattering radiance calculated by the look-up tables (LUTs) in SeaDAS under low-to-moderate solar or viewing zenith angles, and the results show that the relative differences are less than 1.42% when solar zenith angles are less than 70 ∘ and viewing zenith angles are less than 60 ∘. Our SSA-MC model was also compared with the Polarized Coupled Ocean-Atmosphere Radiative Transfer model based on the pseudo-spherical assumption (PCOART-SA), and the results show that the relative differences are mostly less than 2%. At last, based on our SSA-MC model, the effects of Earth curvature on Rayleigh scattering radiance were analyzed for both high solar zenith angles and high viewing zenith angles. The result shows that the mean relative error between the plane-parallel (PP) geometry and spherical shell atmosphere (SSA) geometry is 0.90% when the solar zenith angle is 60 ∘ and the viewing zenith angle is 60.15 ∘. However, the mean relative error increases with increasing solar zenith angle or viewing zenith angle. When the solar zenith angle is 84 ∘ and the viewing zenith angle is 84.02 ∘, the mean relative error is 4.63%. Thus, Earth curvature should be considered in atmospheric corrections at large solar or viewing zenith angles.