An electrochemical process is described wherein a gaseous substance is reduced at the cathode and in which microemulsions of the water-in-oil (w/o) type are utilized as catholytes, said microemulsions showing electric ion transfer and interphase matter transfer capacity. The oil phase of said microemulsion consists of perfluoropolyethers having perfluoroalkyl end groups or hydrophilic functional end groups or of perfluorocarbons and said microemulsions are obtained by using perfluorinated surfactants, in particular those having a perfluoroalkylpolyether structure and/or by using an alcohol as cosurfactant.
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