Carbon materials doped with nitrogen has long been utilized for SO2 removal from flue gases for the benefits of environment. The role of water is generally regarded as hydration of SO3 which is formed through the oxidization of SO2. However, the hydrolysis of SO2, especially on the surface of N doped carbon materials, was almost ignored. In this study, the hydrolysis of SO2 was investigated in detail on the pyridinic nitrogen (PyN) doped graphene (GP) surfaces. It is found that, compared to the homogenous hydrolysis of SO2 assisted with NH3 in gas phase, the heterogeneous hydrolysis is much more thermodynamically and kinetically favorable. Specifically, when a single H2O molecule is involved, the energy barrier for SO2 hydrolysis is as low as 0.15 eV, with 0.59 eV released, indicating the hydrolysis of SO2 can occur at rather low water concentration and temperature. Thermodynamic integration molecular dynamics results show the feasibility of the hydrogenated substrate recovery and the immobilized N acting as a catalytic site for SO2 hydrolysis. Our findings show that the heterogeneous hydrolysis of SO2 should be universal and potentially uncover the puzzling reaction mechanism for SO2 catalytic oxidation at low temperature by N doped carbon materials.