In this work, complex dynamics are found in a fractional-order multi-scroll chaotic system based on the extended Gamma function. Firstly, the extended left and right Caputo fractional differential operators are introduced. Then, the basic features of the extended left Caputo fractional differential operator are outlined. The proposed operator is shown to have a new fractional parameter (higher degree of freedom) that increases the system’s ability to display more varieties of complex dynamics than the corresponding case of the Caputo fractional differential operator. Numerical results are performed to show the effectiveness of the proposed fractional operators. Then, rich complex dynamics are obtained such as coexisting one-scroll chaotic attractors, coexisting two-scroll chaotic attractors, or approximate periodic cycles, which are shown to persist in a shorter range as compared with the corresponding states of the integer-order counterpart of the multi-scroll system. The bifurcation diagrams, basin sets of attractions, and Lyapunov spectra are used to confirm the existence of the various scenarios of complex dynamics in the proposed systems.