A double-volute centrifugal pump is a very important pump type; the internal flow field of a centrifugal pump will change drastically during the transition process of power failure, which will affect the safety and stability of the pump’s operation. In this paper, the CFD numerical simulation method is used, and the UDF procedure is developed to realize the continuous update of the impeller speed at each time step. The working parameters, such as the torque and flow rate at the instantaneous moment, are obtained through the sequential iteration of each small step, and a numerical simulation of the power-off transient is carried out on a double-volute centrifugal pump; additionally, the changes in the external characteristic parameters and the internal flow field of the centrifugal pump are analyzed in detail. The results show that the double-volute centrifugal pump experienced four different modes after power failure, namely pump mode, braking mode, turbine mode, and runaway mode, and the absolute values of the runaway speed and runaway flow rate are 1.465 times and 1.21 times the initial values, respectively. Through the analysis of the flow field in different regions, the change processes of the generation, development, and disappearance of the vortex at each position of the centrifugal pump are obtained, and the change and development processes of the internal velocity gradient of the centrifugal pump are obtained. In addition, it is found that the high-speed area located in the second volute runner is larger than that of the first volute runner because the second volute runner is shorter and narrower than the first volute runner.