Green leaf volatiles play vital roles in plant biotic stress; however, their functions in plant responses to abiotic stress have not been determined. The aim of this study was to investigate the possible role of (Z)-3-hexeny-1-yl acetate (Z-3-HAC), a kind of green leaf volatile, in alleviating the salinity stress of peanut (
Arachis hypogaea L.
) seedlings and the underlying physiological mechanisms governing this effect. One salt-sensitive and one salt-tolerant peanut genotype were primed with 200 μM Z-3-HAC at the 4-week-old stage before they were exposed to salinity stress. Physiological measurements showed that the primed seedlings possessed higher relative water content, net photosynthetic rate, maximal photochemical efficiency of photosystem II, activities of the antioxidant enzymes, and osmolyte accumulation under salinity conditions. Furthermore, the reactive oxygen species, electrolyte leakage, and malondialdehyde content in the third fully expanded leaves were significantly lower than in nonprimed plants. Additionally, we found that application of Z-3-HAC increased the total length, surface area, and volume of the peanut roots under salinity stress. These results indicated that the green leaf volatile Z-3-HAC protects peanut seedlings against damage from salinity stress through priming for modifications of photosynthetic apparatus, antioxidant systems, osmoregulation, and root morphology.