The use of heterogeneous conditions involving Montmorillonite K10 clay was investigated as a mild alternative to homogeneous acidolysis of a lignin model. Guaiacyl Dehydrogenation Oligomers (DHOs) synthesized by horseradish peroxidase were selected as starting material. Hydrolysis products were analyzed by gel permeation chromatography and by HPLC/mass spectrometry. Several experimental parameters were studied such as catalyst and substrate concentration, as well as reaction solvent composition in order to minimize high molar mass product formation generated by recombination mechanisms. In both catalytic modes, the best hydrolysis conditions were similar in terms of solvent composition with dioxane/water (90/10, v/v) and catalyst H(+) concentration of about 0.01 mol/L. Although the homogeneous catalysis generated only 28% of low molecular weight (LMW) products (monomers and dimers), clay catalysis generated 35%. In light of the qualitative analysis, both catalytic methods gave the same products, thus supporting similar hydrolysis mechanisms. (C) 2009 Elsevier Ltd. All rights reserved.