This paper proposes a fractional-order simplest chaotic system using a bi-stable locally-active memristor. The characteristics of the memristor and transient transition behaviors of the proposed system are analyzed, and this circuit is implemented digitally using ARM-based MCU. Firstly, the mathematical model of the memristor is designed, which is nonvolatile, locally-activeand bi-stable. Secondly, the asymptotical stability of the fractional-order memristive chaotic system is investigated and some sufficient conditions of the stability are obtained. Thirdly, complex dynamics of the novel system are analyzed using phase diagram, Lyapunov exponential spectrum, bifurcation diagram, basin of attractor, and coexisting bifurcation, coexisting attractors are observed. All of these results indicate that this simple system contains the abundant dynamic characteristics. Moreover, transient transition behaviors of the system are analyzed, and it is found that the behaviors of transient chaotic and transient period transition alternately occur. Finally, the hardware implementation of the fractional-order bi-stable locally-active memristive chaotic system using ARM-based STM32F750 is carried out to verify the numerical simulation results.