Extracts from acacia, chestnut, cherry, mulberry, and oak wood, used in making barrels for aging wine and spirits were studied by GC/MS positive ion chemical ionization (PICI). Wood chips were extracted by a 50% water/ethanol solution and a tartrate buffer pH 3.2-12% ethanol (model wine) solution. The principal compounds identified in extracts were guaiacol-containing aldehydes and alcohols, such as benzaldehyde and derivatives, vanillin and syringaldehyde, cinnamaldehyde and coniferaldehyde, eugenol and methoxyeugenol, guaiacol and methoxyguaiacol derivatives. PICI using methane as reagent gas produced a high yield of the protonated molecular ion of volatile phenols, compound identification was confirmed by collision-induced-dissociation (CID) experiments on [M + H](+) species. MS/MS fragmentation patterns were studied with standard compounds: guaiacol-containing molecules were characterized by neutral methyl and methanol losses, benzaldehyde derivatives by CO loss. Acacia wood extracts contained significant syringaldehyde and anisaldehyde, but no eugenol and methoxyeugenol. Significant syringaldehyde, eugenol and methoxyeugenol, and high vanillin were found in chestnut and oak wood extracts; low presence of volatile benzene compounds was found in mulberry wood extracts. Cherry wood extracts were characterized by the presence of several benzaldehyde derivatives and high trimethoxyphenol.