This study investigated the essential oil composition of fresh Panax ginseng root and identified novel compounds from ginseng oil. The oil was divided into five fractions (neutral, basic, phenolic, acidic, and aldehydic). In total, 149 constituents, including 29, 19, and 38 compounds in the basic, phenolic, and aldehydic fractions, respectively, were identified by gas chromatography (GC) and GC-mass spectrometry (MS). The primary constituents of the total ginseng volatile oil were α-humulene (13.91% as a peak area), bicyclogermacrene (13.59%), β-caryophyllene (8.24%), α-neoclovene (7.78%), and α- and β-panasinsenes (5.14% and 7.53%). The primary constituents of the basic fraction were 2-isopropyl-3-methoxypyrazine (35.51%), 3-sec-butyl-2-methoxy-5-methylpyrazine (31.54%), 2-isobutyl-3-methoxypyrazine (8.64%), and 2-methoxy-3-methylpyrazine (8.40%), whereas in the phenolic fraction, these were benzoic (25.40%), octanoic (11.57%), nonanoic (9.16%), propionic (6.35%), and decanoic acids (6.16%). The primary constituents of the aldehydic fraction were 4-(2-furyl)-3-buten-2-one (23.41%), benzaldehyde (10.18%), cis-2-heptanal (9.42%), 3-(α-furyl)-propenal (8.51%), and 2-phenyl-2-butenal (7.28%). Among these, the phenylalkenal compounds, including 2-phenyl-2-butenal, 2-methyl-3-phenyl-2-propenal, 5-methyl-2-phenyl-2-pentenal, 5-methyl-2-phenyl-2-hexenals, 2-phenyl-2-octenal, and 2-phenyl-2-nonenal, were newly identified in this study as ginseng volatile constituents. Furthermore, 2-phenyl-2-nonenal was identified as a plant-based volatile constituent for the first time in this study.