Leuconostoc mesenteroides (L. mesenteroides) has known as an electrogenic probiotic bacterium. However, metabolites related to electro-fermentation in ferments of L. mesenteroides are not unveiled. Electrogenic L. mesenteroides fermentatively metabolized bovine milk to dense ferments with homogeneous particle-size distribution. A non-targeted metabolomics approach was performed on non-fermented and L. mesenteroides-fermented milk. A total of 917 metabolites were identified and quantified by ultra-high performance liquid chromatography (UHPLC)-tandem mass spectrometry (MS-MS). Thirteen prokaryotic metabolic pathways associated with differentially expressed metabolites (DEMs) were revealed through Koto Encyclopedia of Genes and Genomes (KEGG) enrichment analysis. Anthranilic acid (AA) and 3-hydroxyanthranilin acid (3-HAA), potentially as electron donors, and quinolinic acid, an electron donor precursor, in the tryptophan kynurenine pathway were significantly increased in the fermented milk. Histidine, arginine, and riboflavin involved in bacterial survival or bioelectricity production were elevated after fermentation. Results indicate that electrogenic L. mesenteroides can mediate electro-fermentation to transform milk to a new nutritional source which is rich in electron donors reportedly acting as antioxidants.