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Rolling robots often use external electric power or pneumatic drive, which limits the usage of them. A chemical reaction self-driven rolling robot was designed. Reaction liquid and catalyst were placed inside the robot. The gas generated by the chemical reaction pushed the reaction liquid to circulate in the multiple cavities of the robot, changing the center of gravity of the robot to achieve rolling. Gravity valve was designed, which was the key component of rolling robot. The gravity valve can be opened and closed periodically at different angles to control the flow. The gravity valve was made of silicone rubber and copper balls. The structure size of the gravity valve was optimized, and the leakage amount reached the minimum under the conditions of required opening and closing angle. The parameters and conditions of the rolling robot to achieve self-drive were analyzed, and the relationship between the lowest liquid level line, the highest liquid level line, the opening angle and closing angle of the gravity valve was obtained. The body of the rolling robot was made by 3D printing. Rotational angular velocity of the rolling robot was about 2(°)/s. The feasibility of this kind of chemical reaction self-driven rolling robot was verified, and a new idea was provided for the application of chemical reaction self-driven in the field of robots.