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This paper reports the development of a high-sensitivity gas sensor and the demonstration of selectively detecting green leaf volatiles (GLV, here hexanal) released from damaged plant leaves. The developed sensor is a conductivity sensor that utilized a 5.2-nm gap as the key detection site between electrodes. The gap was coated with with customized molecular probes toward binding to hexanal. The fabricated sensor demonstrated the detection of a GLV, hexanal, from the collected gas samples from damaged plant leaves, sorghum. Gas samples were collected into a tedlar bag from a glass jar containing damaged sorghum leaves. When exposed to hexanal concentrations from 77.7 to 5181.3 ppm, it produced output signal changes in resistance by 1.64~4.45 times. The sensor response time was measured as 41.6 min at a hexanal concentration of 77.7 ppm.