High performance green propellant represented by ammonium dinitramide-based liquid propellant and its new ignition method are the research hotspots of space propulsion in the 21st century. Exploring the complex multi-scale physical properties of multi-component ammonium dinitramide-based liquid propellant droplets in the electrical ignition mode has wide application significance for spray, propulsion system design and combustion control. The droplet dynamics behavior and combustion characteristics of propellant droplets at different ignition voltages were studied experimentally. The droplet dynamics behavior during the evaporation process, including violent volume oscillation, approximate steady-state expansion, contraction, secondary expansion, puffing and micro-explosion, have been determined by the generation, growth, and discharge of vapor bubbles. In the initial evaporation process, the heterogeneous nucleation is dominant. As the droplet is continuously heated, homogenization nucleation gradually dominates. The main physical and chemical mechanisms of bubble evolution driven by temperature involve methanol boiling, water overheating, ammonium dinitramide decomposition and combustion reaction between vapor molecules. Increasing the ignition voltage increases the droplet dynamics behavior and the combustion, but promotes the combustion instability. Increasing the ignition voltage increases the ignition delay time, puffing delay time, droplet lifetime, maximum temperature of droplet, and reduces the ignition critical diameter. It is proposed that the method of suppressing the droplet breakup dynamics at decomposition area and enhancing the droplet breakup dynamics at the combustion area are conducive to the combustion control of the thruster in electrical ignition mode. This research provides novel insight into the study of the electrical ignition mechanism of liquid fuels.