In order to support the future thermal control and energy conservation design for the Mars rover, numerical studies on natural convection in CO2 enclosures on Mars’ surface were conducted for both horizontal and vertical enclosures. The parameters are as follows: the atmospheric pressure was 1000 Pa, the gravitational acceleration was 3.62 m/s2, and the Prandtl number was 0.77. The heat flux, temperature, and velocity fields of the CO2 enclosures were obtained with the aspect ratio ranging from 5.56 to 200 and the Grashof number ranging from 430 to 2.6 × 104. It was found that natural convection formed more easily in the horizontal enclosures than that in the vertical enclosures when the enclosures had same thickness. With the increasing thickness of the enclosures, Rayleigh–Bénard convections formed in the horizontal enclosures, while only single-cell convections formed in the vertical enclosures. The heat flux through the horizontal enclosures was greater than that through the vertical enclosures with the same thickness when natural convection formed. The maximum difference between them reached 35.26%, which was illustrated by the field synergy principle. A hysteresis phenomenon of the natural convection dominating the heat transfer was found in the vertical enclosure on Mars’ surface. New values for the critical Grashof number and correlations for the average Nusselt number for both the horizontal and vertical CO2 enclosures on Mars’ surface were also developed.