To overcome the drawbacks of fast charge recombination and the limited visible‐light absorption of semiconductor photocatalysts, N ion irradiation is used to enhance photocatalytic performance of ZnO nanowires. Compared with as‐grown ZnO nanowires, the photocatalytic performance of ZnO under dose of 5 × 1015 cm−2 was efficiently improved because of the bandgap energy decreasing and the introduction of oxygen vacancies defects. On one hand, the reduced bandgap energy improves the easy transfer process of electrons and holes, thus improving the charge separation efficiency, and visible‐light absorption. On the other hand, N ion irradiation increases oxygen vacancy defects and hinders the recombination of photo‐excited electrons and holes. This study has certificated that ion irradiation is an efficient way and created a new insight on the enhancement of photocatalytic activity.