Lignin is one of the most promising renewable sources for aromatic hydrocarbons, while effective depolymerization towards its constituent monomers is a particular challenge because of the structural complexity and stability. Intensive research efforts have been directed towards exploiting effective valorization of lignin for the production of bio-based platform chemicals and fuels. The present contribution aims to provide a critical review of key advances in the identification of exact lignin structure subjected to various fractionation technologies and demonstrate the key roles of lignin structures in depolymerization for unique functionalized products. Various technologies (e.g., thermocatalytic approaches, photocatalytic conversion, and mechanochemical depolymerization) are reviewed and evaluated in terms of feasibility and potential for further upgrading. Overall, advances in pristine lignin structure analysis and conversion technologies can facilitate recovery and subsequent utilization of lignin towards tailored commodity chemicals and fungible fuels.