In this paper, the combination of hyphenated chromatography and chemometric resolution was investigated as a method to qualitatively and quantitatively determine volatile components in Cortex cinnamomi from four main producing areas. With the help of chemometric resolution approaches, whether the chromatographic elution of chemical components is featured by "first-in-first-out" or embedded peaks could be determined. Upon this useful information obtained, the matrix data generated by hyphenated chromatography could be uniquely resolved into pure chromatogram and spectrum of each chemical component involved followed by qualitative and quantitative analysis. The results obtained in this work showed that, 94, 88, 93 and 89 volatile components were separated and 63, 60, 60 and 58 of them qualitatively and quantitatively determined representing about 93.39, 93.62, 92.03 and 92.59% of the total relative content, respectively. The combination of hyphenated chromatography with chemometric resolution could greatly enhance the chromatographic separation and spectral qualitatively determination ability so as to qualitatively and quantitatively detect many more volatile components and improve the analysis accuracy.