Decomposition of hydroxylammonium nitrate (HAN) solution with electrolytic decomposition method has attracted much attention in recent years due to its efficiencies and practicability. However, the phenomenon has not been well-studied till now. By utilizing mathematical model currently available, the effect of water content and power used for decomposition was studied. Experiment data shows that sacrificial material such as copper or aluminum outperforms inert electrodes in the decomposition of HAN solution. In the case of using copper wire to electrolyse HAN solutions, approximately 10 seconds is required to reach 100 °C regardless of concentration of HAN. In term of power consumption, 100 W–300 W was found to be the range in which decomposition could be triggered effectively using copper wire as electrodes.