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Hydrogen peroxide (H₂O₂) can be considered as a sterilant or a green propellant. For a common use in industrial application, spray is an effective method to form fine H₂O₂ droplets. In this paper, electrostatic atomization based on the configuration of needle ring electrodes is proposed to produce H₂O₂ spray by minimizing its effective surface tension. The breakup performances of H₂O₂ ligaments can be improved by increasing the electric field intensity, reducing the nozzle size, and adjusting suitable volume flow rate. The smallest average diameter of breakup droplets for 35 wt. % concentration H₂O₂ solution reached 92.8 μm under optimum operation conditions. The H₂O₂ concentration significantly influenced the breakup performance owing to the concentration effect on comprehensive physical properties such as density, surface tension, viscosity, and permittivity. The average diameters of breakup droplets decreased with decreasing H₂O₂ concentration. At 8 wt. % concentration, the average breakup droplet diameter was reduced to 67.4 μm. Finally, electrostatic atomization mechanism of H₂O₂ solution was analyzed by calculating dimensionless parameters of <i>Re</i>, <i>We</i>, and <i>Oh</i> numbers with the combination of the operation conditions and physical properties for in-depth understanding the breakup behaviors. The calculation showed that the minimum average diameter of breakup droplets was obtained at 8 wt. % concentration at the investigated range of H₂O₂ concentration, which kept in agreement with the experimental results.