This paper sets up a complete CO2 contact angle test system by a visualization autoclave, uses the hanging drop-method respectively getting the advancing angle and receding angle of CO2, on the shale surface under the different temperature, and uses the Snake method measuring contact angle of droplet images, to make the wettability experimental study for CO2 on the shale surface. According to contact angle data, wettability of CO2 on the shale surface is preferable; the temperature is the higher, the wettability is better. At the same time, by analyzing correspondingly with scanning electron microscope images of shale sample, it is obtained that shale with different surface structures has affected wettability of CO2.