Chaotic systems depict complex dynamics, thanks to their nonlinear behaviors. With recent studies on fractional-order nonlinear systems, it is deduced that fractional-order analysis of a chaotic system enriches its dynamic behavior. Therefore, the investigation of the chaotic behavior of a 4D memristive Chen system is aimed in this study by taking the order of the system as fractional. The nonlinear behavior of the system is observed numerically by comparing the fractional-order bifurcation diagrams and Lyapunov Exponents Spectra with 2D phase portraits. Based on these analyses, two different fractional orders (i.e., q = 0.948 and q = 0.97) are determined where the 4D memristive system shows chaotic behavior. Furthermore, a single state fractional-order sliding mode controller (FOSMC) is designed to maintain the states of the fractional-order memristive chaotic system on the equilibrium points. Then, control method results are obtained by both numerical simulations and different illustrative experiments of microcontroller-based realization. As expected, voltage outputs of the microcontroller-based realization are in good agreement with the time series of numerical simulations.