Abstract: The numerical simulation was performed on liquid sodium laminar natural convection in square cavity. The distribution characteristics of heat transfer coefficient were obtained, and the effect was emphasized on the analysis of the impact of Rayleigh number upon the natural convective heat transfer process in a square cavity under different thermal boundary conditions. The results show that the liquid sodium natural heat transfer process is greatly influenced by the Rayleigh number when Rayleigh number is large enough. While when Rayleigh number is smaller than, say 103, the distributions of natural convective heat transfer coefficients on both the side walls and the bottom wall of the square cavity are almost the same as those of conductive heat transfer process, respectively. This means that the mechanisms of heat transfer process mainly depend on heat conduction under cases with lower Rayleigh number.