With the increasing emphasis on fire safety requirements, perfluorohexane fire extinguishing agents have found innovative applications in power distribution systems due to their unique properties. This article discusses the characteristics and advantages of perfluorohexane materials, as well as the application forms of perfluorohexane in power distribution systems. Based on this, a fire extinguishing test was conducted using a specific power distribution system as an example, simulating the initial stage of an indoor power distribution system fire. Gas concentrations of CO, NO, SO₂, and O₂ were measured before and after the fire, and the patterns of temperature and thermal radiation changes at different locations within the fire scene were analyzed. Perfluorohexane fire extinguishing agent was used to suppress the fire in the power distribution system. The test results indicate that in distribution system fires, perfluorohexane extinguishing agents have a fast extinguishing speed, capable of quickly extinguishing fires within 8 seconds, with significant heat absorption and cooling effects, achieving a cooling rate of up to 97.8°C/min. the concentrations of several gases decreased by 65.4% to 100% within a short time, and it did not cause any damage to the power distribution system. This achieved controllable fire suppression and improved extinguishing efficiency in power distribution system fires, representing a new approach to the suppression of initial fires in power distribution systems.