Fractional-order systems have been applied in many engineering applications. A key issue with the application of such systems is the approximation of fractional-order parameters. The numerical tools for the approximation of fractional-order parameters gained attention recently. However, available toolboxes in the literature do not have a direct option to approximate higher order systems and need improvements with the graphical, numerical, and stability analysis. Therefore, this chapter proposes a MATLAB-based GUI for the approximation of fractional-order operators. The toolbox is made up of four widely used approximation techniques, namely, Oustaloup, refined Oustaloup, Matsuda, and curve fitting. The toolbox also allows numerical and stability analysis for evaluating the performance of approximated transfer function. To demonstrate the effectiveness of the developed GUI, a simulation study is conducted on fractional-order PID control of pH neutralization process. The results show that the toolbox can be effectively used to approximate and analyze the fractional-order systems.