The experimental device for carrying out chemical reactions in charged microdroplets with the accumulation of reaction products and reactants in a liquid electrode was developed. The fundamental possibility of electrospraying a liquid onto the surface of a polar liquid (using acetonitrile as an example) in the modes of both positively and negatively charged microdroplets generation has been shown. In the mode of positively charged microdroplets generation, acidified acetonitrile was used as a sprayed solution; in the mode of negatively charged microdroplets generation, pure acetonitrile was used. In both cases, a stable electrospray mode was obtained over a wide range of the spraying voltage U (from 2.2 kV to 5 kV), the distance from the spraying capillary to the surface of the liquid electrode L (from 3 mm to 23 mm) and the sprayed solution feed rate Q (from 25 μl/min to 200 μl/min). It was shown on the example of the reaction of phenylhydrazine with anisic aldehyde that the products of reactions occurring in charged microdroplets, as well as the reactants, accumulate in the volume of the liquid electrode.