Hydroxyl radical has been widely applied in the non-food fields, but whether its feasibility for treating fruits and vegetables remains unknown. In this work, effects of hydroxyl radical water (HRW) treatment on functional components, volatile compounds, and preservation properties of cherry tomato, grape, coriander and celery were investigated. Results showed that HRW treatment could be significantly effective on delaying the color change and decay of fruits and vegetables. Besides causing a slim loss of total sugars, HRW-treated samples exhibited different losses of total phenols and ascorbic acid. The total phenol and ascorbic acid of celery were lost by 17.95% and 13.01% respectively, which may be caused by excessive surface area, indicating that the applicability of HRW to celery is still to be discussed. The loss of functional components of both fruits could be controlled under 4%. Phenolic profiles and volatile compounds kept almost steadily during treatment. Notably, the increased contents of partial ester compounds might improve the sensory of fruits and vegetables, cherry tomatoes treated with HRW showed an increase of 77.28% in ethyl caproate. Moreover, the reduction of some compounds obtained from the decomposition of fatty acid hydroperoxides may enhance the fresh odor of fruits and vegetables. Accordingly, HRW treatment is a safety and environmental technology for post-harvest processing of fruits and vegetables.