The changes of volatile composition and other quality traits of blueberry during postharvest storage were investigated. Blueberries were packaged in vented clam-shell containers, and stored at 0 °C for 0, 15 and 60 days, followed by storage at room temperature (25 °C) for up to 8 days for quality evaluation. The firmness, pH, and total soluble solids increased by 8.42%, 8.92% and 42.9%, respectively, after 60 days of storage at 0 °C. Titratable acidity decreased 18.1% after 60 days of storage at 0 °C. The volatile change was monitored using headspace–solid-phase microextraction–gas chromatography–quadrupole time-of-flight–mass spectrometry (HS-SPME-TOF-MS) and off-odor was evaluated by sensory panel. Volatile compounds generally showed a downward trend during cold storage. However, the subsequent shelf life was the most remarkable period of volatile change, and was represented by the strong fluctuation of ethyl acetate and the rapid decrease of terpenoids. Extending storage from 15 to 60 days under cold condition still resulted in an acceptable odor. However, subsequent storage at higher temperature resulted in a quick deterioration in sensory acceptability. The results proved that cold storage was a reliable way to maintain the quality of blueberry, and flavor deterioration during subsequent shelf life was more fatal to the blueberry flavor.