A new reliability assessment methodology is presented and the new method is compared with fault tree analysis. The system is modeled by directed graph at a new methodology, which is composed of nodes and arcs. The directed graph corresponds to the layout of chemical process and is easy to construct. Therefore, the directed graph analysis is applicable to the chemical process that has complex sequence. The example of fault tree analysis and directed graph analysis is given. The directed graph analysis has proved to be a valuable and useful method for the reliability assessment of chemical process.