In this article, we develop a numerical method based on the operational matrices of shifted Vieta–Lucas polynomials (VLPs) for solving Caputo fractional-order differential equations (FDEs). We derive a new operational matrix of the fractional-order derivatives in the Caputo sense, which is then used with spectral tau and spectral collocation methods to reduce the FDEs to a system of algebraic equations. Several numerical examples are given to show the accuracy of this method. These examples show that the obtained results have good agreement with the analytical solutions in both linear and non-linear FDEs. In addition to this, the numerical results obtained by using our method are compared with the numerical results obtained otherwise in the literature.