Off-odours caused by volatile organic compounds (VOCs) are often the first indicators consumers have of milk spoilage. In this study the VOCs associated with three types (trim, 0.25–0.40% fat; lite, 1.40–1.50% fat; and full-cream, 3.18–3.28% fat) of fresh chilled pas-teurised milk (FCPM), held for up to 17 days at 4.5 _ 0.5 8C, were measured using proton- transfer-reaction mass spectrometry (PTR-MS). The chemical identification of VOCs in the headspace of the milk was supported by SPME–GC–MS analysis. Bacterial numbers (aerobic plate count at 25 8C) in the milk were also estimated. Replicate sets of milk types treated with sodium azide (NaN3) to inhibit microbial activity were investigated. The relationship between microbial numbers and VOCs was not linear; rather the concentrations of VOCs only started to change after a threshold number of bacteria ranging from 106–108 CFU mL_1 was reached. This combined approach provided new insights on the effect of microbial growth on FCPM shelf-life.