This study aimed to utilize a novel modified approach based on teaching–learning-based optimization (MTLBO), to achieve an approximate solution of optimal control problem governed by nonlinear Volterra integro-differential systems. The scheme was based upon Chebyshev wavelet and its derivative operational matrix, which eventually led to a nonlinear programming problem (NLP). The resulted NLP was solved by the MTLBO. The novel algorithm used a heuristic mechanism to intensify learning on the best students in learner phase. The new strategy was applied to improve learners’ knowledge and to structure the MTLBO. The applicability and efficiency of the MTLBO were shown for three numerical examples. The proposed algorithm was compared with the traditional TLBO algorithm and the Legendre wavelets and collocation method in the literature. The experimental results showed that the proposed MTLBO not only obtained the high-quality solutions with respect to the absolute errors but also provided results with the high speed of convergence.