Green leaf volatiles (GLVs), which include C6 aldehydes, alcohols, and their esters, are emitted by damaged plants and are, therefore, thought to be involved in stress responses. However, the effects of GLVs on gene expression are not fully understood. Thus, the aim of the present study was to analyze the early transcriptional responses of Arabidopsis to the major GLVs-(Z)-3-hexenal, (Z)-3-hexenol, (E)-2-hexenal, and (Z)-3-hexenyl acetate-using comprehensive microarray gene expression analysis. All of the GLVs induced changes in gene expression, and (Z)-3-hexenal, (Z)-3-hexenol, and (Z)-3-hexenyl acetate commonly triggered the expression of defense-related genes, whereas (E)-2-hexenal mainly induced genes responsible for responding to abiotic stress, such as heat and oxidative stress. These results suggest that GLVs can function as airborne infochemicals that regulate the rapid expression of defense response-related genes and that GLVs might play a physiological role as self-made damage-associated molecular patterns (DAMPs) in damaged leaves.