The graph theoretical analysis and a graph's characteristic polynomial are deployed as the basis for a system approach employed to develop a model for estimating the reliability index and evaluating the availability index for a coal-fired generating power station. In this research, the coal-fired generating station system is divided into six subsystems. Elementary to evaluating the reliability (estimate) of the said system is the consideration of all the subsystems and their interrelations. Approximate reliability attributes of the graph are used to model the approximate reliability of the coal-fired generating station. Subsystem reliability is represented by the nodes in the graph, and the links represent the reliability of interrelations of these subsystems. Computing a graph's characteristic polynomial using three different methods, namely, the linearly independent cycles, the figure equation and the adjacent matrix, the approximate reliability of the system is determined. Three methods are used, for comparison purposes, as estimating reliability is always an imperfect endeavour. The methodology proposed in this study is illustrated step-by-step with the help of examples.