Comprehensive two-dimensional gas chromatography (GCxGC) is a novel technique which is rapidly gaining importance for the analysis of complex samples. In the present review, attention is devoted to the principle and advantages, and main characteristics such as modulation, column combinations, detector requirements and data processing, of the technique. Specifically, GCxGC of a variety of real-life samples is discussed to demonstrate the applicability of the technique, with emphasis on the usefulness of the ordered-structure principle and on the analyte-identification power provided by a combination with time-of-flight mass spectrometric detection.