Raman and 13C NMR spectroscopies have been applied to characterise the ethyl xanthate compounds of potassium, sodium, copper, silver, and gold, and diethyl dixanthogen in order to provide a basis for investigating the interaction of ethyl xanthate with metal surfaces. Spectra for the various species in the solid state obtained by both techniques are interpreted in terms of molecular conformation and differences in atomic environments in the crystal structure. Spectra for potassium ethyl xanthate in aqueous solution provide evidence of hydrophobic interaction between the hydrocarbon moiety and water. Raman spectroscopy provides an effective means of distinguishing between dixanthogen and metal xanthates.