A new electrolyzed water-CaCl2-HCl electrolyzed water (CHEW) was obtained by combining slightly acidic electrolyzed water and calcium. The objective of this study was to explore the effect of preharvest CHEW treatment on the quality during storage of broccoli sprouts. Preharvest CHEW treatment not only reduced the electrolyte leakage, reactive oxygen species, weight loss and the number of microorganisms during storage of broccoli sprouts, but also slowed down the breakdown of cell structure and maintained color and textural properties of broccoli sprouts. Besides, preharvest CHEW treatment reduced the degradation of active substances in broccoli sprouts during storage. The contents of important bioactive compounds in broccoli sprouts-glucoraphanin and sulforaphane, along with the enzymatic activity and genes involved in glucosinolates metabolism have also been further investigated. On day 12 of storage, compared to preharvest tap water treatment, the contents of glucoraphanin and sulforaphane in broccoli sprouts with preharvest CHEW treatment increased by 63% and 128%, respectively. Meanwhile, the generation of offensive odors in broccoli sprouts during storage was also inhibited under preharvest CHEW treatment. In general, preharvest CHEW treatment maintained the good quality during storage and prolong the shelf life of broccoli sprouts, which provides a new perspective for postharvest preservation of broccoli sprouts.