Berries of six Vitis davidii Foex (spine grape) cultivars (‘Baiputao’, ‘Gaoshan 1’, ‘Gaoshan 2’, ‘Seputao’, ‘Miputao’, and ‘Tianputao’) were harvested from a commercial vineyard in Hunan Province in China. Free and bound volatile compounds and fatty acids were analyzed by GC–MS, and amino acids were analyzed by HPLC. ‘Tianputao’ and ‘Miputao’ were characterized by relatively higher concentrations of aromatic amino acids and lower concentrations of branched-chain amino acids. The major free volatile compounds of spine grapes were hexanal, (E)-2-hexenal, 1-hexanol, (E)-2-hexenol, (E)-β-damascenone, and benzeneacetaldehyde. The major glycosidically bound volatile compounds identified were 1-hexanol, menthol, nerol, 1-butanol, 3-methyl-3-butenol, benzenemethanol, β-phenylethanol, eugenol, and guaiacol. (E)-β-damascenone, benzeneacetaldehyde, guaiacol, and eugenol had odor activity values (OAVs) > 1 in all cultivar grapes. Partial least squares discriminant analysis (PLS-DA) revealed ‘Tianputao’ to be distinct from the other cultivars due to its relatively higher concentrations of major terpenoids, norisoprenoids, higher alcohols, and aromatic amino acids.