The practicability and potential of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOF-MS) for the analysis of complex flavour mixtures in food were studied. With the determination of key flavour targets in dairy samples as an example, it was demonstrated that GC×GC dramatically improves the separation. As a consequence, identification and, more importantly, quantification down to the ng/g level can be performed more reliably: background interferences largely disappear. Next to the peak table generated from the GC-TOF-MS software after data processing, the additional use of well-ordered patterns in the 2D-plane and information from second-dimension retention times can substantially help the identification of unknowns. The technique was successfully used for an evaluation of extraction techniques and the characterisation of different types of samples. © 2003 Published by Elsevier B.V.