The movement presented by chaos is violent oscillation, making the system unstable, which often is harmful in engineering. Therefore, how to suppress chaotic state quickly is a research hotspot in the field of control. Compared with integer-order system, fractional-order chaotic system has more complex dynamic characteristics, and it is often difficult to control the dynamic system into a stable periodic motion. In this paper, a new sliding mode controller was proposed after newly constructing a fractional-order chaotic system, to make the chaotic system enter a predetermined motion state quickly and maintain stability. Firstly, a new five-dimensional fractional-order chaotic system was constructed, analyzing its dynamic characteristics through the 0–1 test. Then, a sliding mode controller was designed, with proved stability to regulate the motion state of chaotic system. Finally, the circuit realization and control process simulation of the five-dimensional fractional-order chaotic system were carried out. The experimental results show that the proposed sliding mode controller has simple structure, but fast response and excellent control effect.