Lignin is a substantial component of lignocellulosic biomass but is under-utilized relative to the cellulose and hemicellulose components. Historically, lignin has been burned as a source of process heat, but this heat is usually in excess of the process energy demands. Current models indicate that development of an economically competitive biorefinery system requires adding value to lignin beyond process heat. This addition of value, also known as lignin valorization, requires economically viable processes for separating the lignin from the other biomass components, depolymerizing the lignin into monomeric subunits, and then upgrading these monomers to a value-added product. The fact that lignin’s biological role is to provide biomass with structural integrity means that this heteropolymer can be difficult to depolymerize. However, there are chemical and biological routes to upgrade lignin from its native form to compounds of industrial value. Here we review the historical background and current technology of (thermo) chemical depolymerization of lignin; the natural ability of microbial enzymes and pathways to utilize lignin, the current prospecting work to find novel microbial routes to lignin degradation, and some applications of these microbial enzymes and pathways; and the current chemical and biological technologies to upgrade lignin-derived monomers.