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We report enhanced electrochemical detection of single water-in-oil emulsion droplets using the nano-impact method. To detect the emulsion droplets, the water molecules in the droplets were directly oxidized (i.e., water splitting) without additional electroactive species when the droplets collided with the ultramicroelectrode. The water molecules in the emulsion droplet cannot be directly electrolyzed in an organic solvent because the emulsifier does not require a hydrophobic electrolyte. To enhance the signal intensity, the electrochemistry of sub-microscale single droplets was investigated considering the charge neutrality and limiting reagent. Therefore, effective electrolysis of the droplets was achieved. Approximately 10% of water molecules in the droplet (55.6 M H2O) were oxidized based on calculations from the electrochemical peak analysis and DLS measurements. [ABSTRACT FROM AUTHOR]