The effect of oxygen-vacancy-related defects on gas-sensing properties of ZnO-nanowire gas sensors was investigated. Gas sensors were fabricated by growing ZnO nanowires bridging the gap between two prepatterned Au catalysts. The sensor displayed fast response and recovery behavior with a maximum sensitivity to NO2 gas at 225 °C. Gas sensitivity was found to be linearly proportional to the photoluminescence intensity of oxygen-vacancy-related defects in both as-fabricated and defect-controlled gas sensors by postannealing in Ar and H2 atmosphere. This result agrees well with previous theoretical prediction that oxygen vacancies play a role of preferential adsorption sites for NO2 molecules.