In this paper, we state an efficient method for solving the fractional Riccati differential equation. This equation plays an important role in modeling the various phenomena in physics and engineering. Our approach is based on operational matrices of fractional differential equations with hybrid of block-pulse functions and Chebyshev polynomials. Convergence of hybrid functions and error bound of approximation by this basis are discussed. Implementation of this method is without ambiguity with better accuracy than its counterpart other approaches. The reliability and efficiency of the proposed scheme are demonstrated by some numerical experiments.