Hydrogenolysis has emerged as one of the most effective means of converting polymeric lignin into monoaromatic fragments of value. Reported yields may be higher than for other methods and can exceed the theoretical yields estimated from measures of the content of lignin's most readily cleaved alkyl-aryl ether bonds in beta-ether units. The high yields suggest that other units in lignin are being cleaved. Diaryl ether units are important units in lignin, and their cleavage has been examined previously using simple model compounds, such as diphenyl ether. Herein, the hydrogenolysis of model compounds that closely resemble the native lignin 4-O-5 diaryl ether units was analyzed. The results provided unexpected insights into the reactivity and partial cleavage of these compounds. The models and lignin polymer produced not only monomers, but also unusual 1,3,5-meta-substituted aromatics that appear to be diagnostic for the presence and the cleavage of the 4-O-5 diaryl ether unit in lignin.