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Abstract The green leaf volatiles (GLVs)Z‐3‐hexen‐1‐ol (Z3‐HOL) andZ‐3‐hexenyl acetate (Z3‐HAC) are airborne infochemicals released from damaged plant tissues that induce defenses and developmental responses in receiver plants, but little is known about their mechanism of action. We found that Z3‐HOL and Z3‐HAC induce similar but distinctive physiological and signaling responses in tomato seedlings and cell cultures. In seedlings, Z3‐HAC showed a stronger root growth inhibition effect than Z3‐HOL. In cell cultures, the two GLVs induced distinct changes in MAP kinase (MAPK) activity and proton fluxes as well as rapid and massive changes in the phosphorylation status of proteins within 5 min. Many of these phosphoproteins are involved in reprogramming the proteome from cellular homoeostasis to stress and include pattern recognition receptors, a receptor‐like cytoplasmic kinase, MAPK cascade components, calcium signaling proteins and transcriptional regulators. These are well‐known components of damage‐associated molecular pattern (DAMP) signaling pathways. These rapid changes in the phosphoproteome may underly the activation of defense and developmental responses to GLVs. Our data provide further evidence that GLVs function like DAMPs and indicate that GLVs coopt DAMP signaling pathways.