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Previous work has demonstrated that slightly acidic electrolyzed water (SAEW) can promote growth and nutrient enrichment of buckwheat sprouts. In this study, iTRAQ-based quantitative proteomic analysis of SAEW-induced buckwheat sprouts was conducted to explore its mechanism of action. The results showed that 11, 10 and 14 differentially expressed proteins (DEPs) related to energy metabolism, oxidative stress and flavonoid biosynthesis accumulated upwards and downwards, respectively, in SAEW-treated buckwheat. Bioinformatics analysis revealed 118 GO categories were in relation to molecular function. In the SAEW group, a total of 9 DEPs (5 up-regulated) were mapped to 10 significantly enriched KEGG pathways. SAEW induced flavonoid enrichment by modulating zymoproteins (e.g. phenylalanine ammonialyase and flavonol synthase) in phenylpropanoid biosynthesis pathway. qRT-PCR results had consistency with abundance levels of their corresponding proteins. These findings are likely to reveal the molecular mechanisms underlying the biochemical enrichment of buckwheat sprouts by SAEW.