Lignin’s aromatic building blocks provide a chemical resource that is, in theory, ideal for substitution of
aromatic petrochemicals. Moreover, degradation and valorization of lignin has the potential to generate
many high-value chemicals for technical applications. In this study, electrochemical degradation
of alkali and Organosolv lignin was performed using the ionic liquids 1-ethyl-3-methylimidazolium
trifluoromethanesulfonate and triethylammonium methanesulfonate. The extensive degradation of
the investigated lignins with simultaneous almost full recovery of the electrolyte materials provided
a sustainable alternative to more common lignin degradation processes. We demonstrate here that
both the presence (and the absence) of water during electrolysis and proton transport reactions had
significant impact on the degradation efficiency. Hydrogen peroxide radical formation promoted certain
electrochemical mechanisms in electrolyte systems “contaminated” with water and increased yields of
low molecular weight products significantly. The proposed mechanisms were tentatively confirmed by
determining product distributions using a combination of liquid chromatography-mass spectrometry
and gas-chromatography-mass spectrometry, allowing measurement of both polar versus non-polar as
well as volatile versus non-volatile components in the mixtures