This paper presents a new hybrid approach that combines Modified Priority List (MPL) with Charged System Search (CSS), termed MPL-CSS, to solve one of the most crucial power system's operational optimization problems, known as unit commitment (UC) scheduling. The UC scheduling problem is a mixed-integer nonlinear problem, highly-dimensional and extremely constrained. Existing meta-heuristic UC solution methods have the problems of stopping at a local optimum and slow convergence when applied to largescale, heavily-constrained UC applications. In the first step of the proposed method, initial hourly optimum solutions of UC are obtained by Modified Priority List (MPL); however, the obtained UC solution may still be possible to be further improved. Therefore, in the second step, the CSS is utilized to achieve higher quality solutions. The UC is formulated as mixed integer linear programming to ensure the tractability of the results. The proposed method is successfully applied to a popular test system up to 100 units generators for both 24-hr and 168-hr system. Computational results show that both solution cost and execution time are superior to those of published methods.