The solidification sequence during the solidification of fusion-cast explosives is an important parameter for the optimization of the manufacturing process, which can be analyzed by using numerical simulation experiments. However, the numerical simulations are not totally reliable due to the inherent errors in the algorithms and parameters. To address this issue, a measurement method is proposed to monitor the solidification process based on the embedded method of distributed fiber optic sensing. And a method is developed to identify the solid–liquid phase change interface region, which can be effectively demodulated and analyzed for sensing data. The experimental results were verified by using numerical simulations based on casting simulation software and compared. It can be found that the total solidification time and pattern of both are relatively consistent. However, some of the solidification characteristics in the numerical simulation are lack of precision due to the inaccuracy of the heat transfer parameters.