Supercritical carbon dioxide (SC-CO 2 ) fluid can dissolve surface matter on shale and, thus, change the surface properties of shale. To study the influence of SC-CO 2 on the water wettability of shale, shale samples collected from the Longmaxi formation in Sichuan Basin were treated with SC-CO 2 at various time intervals, pressures, and temperatures. The results show that, after SC-CO 2 treatment, the ratio of C and Si in the shale increased, while the ratio of O, Ca, Mg, and H decreased. Water was released from the clay minerals, and the CaCO 3 content decreased in the shale. After SC-CO 2 treatment, the primary pores and fractures in the shale were eroded through dissolution and new pores and fracture structures were developed on the surface microstructure of the shale. As a result, the structure connectivity, which favored the seepage of shale gas, was improved. The results also show that the shale−water contact angles were increased after SC-CO 2 treatment. The treatment time and pressure had a significant influence on the contact angles, but the effect of the treatment temperature on contact angles was not obvious. The change in the contact angles resulted from a reduction of the CaCO 3 content on the shale surface, which decreased the surface hydrophilicity. The shale surface water wettability and the shale surface tension were decreased after SC-CO 2 treatment. This reduces the hindrance function of water in the shale minimal pores and fracture, which is beneficial to CO 2 diffusion into the shale matrix. This promotes CO 2 adsorption capacity in the shale as well as CH 4 desorption from the shale. This study provides a theoretical basis for using SC-CO 2 fluid for efficient shale gas exploitation in the Longmaxi formation of the Sichuan Basin.