The perishable nature of horticultural products and unfavorable factors during storage lead to postharvest losses and shelf life limitations. As an effective hydrogen (H2) supplier, hydrogen-rich water (HRW) is regarded as a new green postharvest preservation strategy of horticultural products. This review presents a complete overview of the application advance of HRW for the preservation of horticultural products, including the potential production mechanisms of hydrogen in plants, the preparation and application methods of HRW, and potential mechanisms of HRW in improving the quality of postharvest horticultural products. The findings show that HRW can maintain the quality and stress tolerance of horticultural products by regulating metabolic pathways and molecular responses, including oxidative defense, energy homeostasis, respiration, cell-wall intergrity, ethylene biosynthesis, related gene expression and phytohormones signaling crosstalk. The information obtained in this review is expected to provide a scientific basis for the application of HRW for the preservation of postharvest horticultural products.