Arylglycerol-ether bonds of lignin samples or model compounds vera selectively cleaved by treatment with dioxane-ethanethiol (9/1, v/v) and 0.2 N HBF4etherate or 0.2 N BF3etherate at 100°C for four hour3. Monomers resulting from “thioacidolysis” were identified by gas chroraatography-mass spectrometry of their trimethylslly derivatives. Compared to acidolysls (dloxane-water, 0.2 N HCL, 100°C 4h), thioacidolysis yields less complex mixtures of monomers. The monomer yields for lignin thioacidolysis were also higher than for acidolysls. This increase was particularly evident for hardwood lignins.