Comprehensive 2-D GC (GC x GC) coupled with TOF MS or flame ionization detector (FID) was employed to characterize and quantify the chemical composition of volatile oil in the radixes of Panax ginseng C. A. Mey. (ginseng) at different ages. Thirty-six terpenoids were tentatively identified based on the MS library search and retention index in a ginseng sample at the age of 3 years. An obvious group-type separation was obtained in the GC x GC-TOF MS chromatogram. The data collected by GC x GC-FID were processed using a principal component analysis (PCA) method to classify the samples at different ages. The compounds responsible for the significant differentiation among samples were defined. It was found that the relative abundances of alpha-cadinol, alpha-bisabolol, thujopsene, and n-hexadecanoic acid significantly rise with the increase in age.