Gas chromatography time-of-flight mass spectrometry was applied to elucidate the profiling of primary metabolites and to evaluate the differences between quality differences in Angelica acutiloba (or Yamato-toki) roots through the utilization of multivariate pattern recognition-principal component analysis (PCA). Twenty-two metabolites consisting of sugars, amino and organic acids were identified. PCA analysis successfully discriminated the good, the moderate and the bad quality Yamato-toki roots in accordance to their cultivation areas. The results signified two reducing sugars, fructose and glucose being the most accumulated in the bad quality, whereas higher quantity of phosphoric acid, proline, malic acid and citric acid were found in the good and the moderate quality toki roots. PCA was also effective in discriminating samples derive from different cultivars. Yamato-toki roots with the moderate quality were compared by means of PCA, and the results illustrated good discrimination which was influenced most by malic acid. Overall, this study demonstrated that metabolomics technique is accurate and efficient in determining the quality differences in Yamato-toki roots, and has a potential to be a superior and suitable method to assess the quality of this medicinal plant.