Introduction: Radix Angelicae sinensis (Danggui, DG) is known as one of the typical traditional Chinese medicines. DG material consists of a variety of volatile substances, polysaccharides, organic acids, ceramides, amino acids, vitamins, microelements, among others, and thus has been used for medicinal and edible purposes in a long history. The fragrance is of importance to assessing the DG material quality. Objectives: This study was to determine volatile flavour compositions of DG materials and to reveal the odour complexity. Material and methods: Electronic nose (E-nose), integrated gas chromatographymass spectrometry/olfactometry (GC-MS/O) and comprehensive two-dimensional gas chromatography-time-of-flight-mass spectrometry (GC Â GC-TOF-MS), combined with solid-phase micro-extraction (SPME), were mainly used to address the flavour complexity of DG materials. Results: Using the E-nose sensor responses, a total of 105 batches of DG samples cultivated in six provinces of China were categorised according to their odour differentiations, and a principal component analysis (PCA) model was established for evaluating the sample quality through a combination of Hotelling's T 2 and Q-residual values in a statistical quantitative sense. By the GC-MS/O and GC Â GC-TOF-MS analyses, 196 volatile flavour compounds were identified, 51 odour-active areas discerned and 39 odourants determined. It was terpenes and aromatics of the flavour compounds that mainly contributed to the odour attributes of DG herb. Conclusion: The SPME-GC Â GC-TOF-MS method was the first time employed to analyse the volatile flavours of DG materials, and thus made a breakthrough in determining 196 flavour compounds, much more than those in any previous report. The work also made a significant step forward to link the flavour compositions and odour complexity of radix Angelicae sinensis by E-nose and GC-MS/O techniques. It not only provided a statistical PCA model that did not depend on any predetermined