Transitioning from crude oil to renewable sources of carbon-based chemicals is critical for advancing sustainable development. Lignin, a wood-derived biomacromolecule, holds great potential as a renewable feedstock, but efficient depolymerization and dearomatization methods are required to fully unlock its potential. In this investigation, we present a silver-catalyzed aqueous electrocatalytic method for the selective depolymerization and partial dearomatization of soda lignin under mild, ambient conditions. Utilizing a water/sodium carbonate solvent system and a silver electrode to mediate the electrochemical reduction, we achieved significant lignin depolymerization over reaction times ranging from 5 to 20 h. Analysis by nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HRMS) revealed sodium levulinate, sodium acetate, and sodium formate as the main aliphatic products, alongside various aromatic species in the depolymerized lignin products (DL). This selective conversion of lignin into both valuable aromatic compounds and reactive aliphatic intermediates offers promising opportunities for further synthesis of a wide range of organic chemicals, contributing to the development of a more sustainable and circular economy.