Ceramides play a critical role in the skin barrier. We previously demonstrated that electrolytic-reduction ion water (ERI) improves skin integrity and enhances the protective barrier function of the epidermis. Here, we first examine the effect of ERI on the expression of ceramide synthesis–related enzymes in human skin keratinocytes. The expression of enzymes involved in the elongation of very-long-chain fatty acids protein 4 (ELOVL4) was increased after treatment with ERI-containing media. The expression of ceramide synthase 3 (CerS3), which binds ultra-long-chain fatty acids to sphingosine to produce ceramides found in the skin, was also increased. Subsequently, we examined the expression of ceramides in keratinocytes treated with ERI using thin-layer chromatography. The results showed that ERI increased the ceramide content, and these ceramides were more hydrophobic than those extracted from untreated keratinocytes. These results suggest that ERI enhances the expression of enzymes involved in the synthesis of ceramides containing ultra-long-chain fatty acid residues, which have a protective function in the skin.