Lignin is the second most abundant renewable material after cellulose. However, its economic use is currently relegated to low-value energy production. This biomaterial holds great potential as a source of renewable biofuels, bio-based chemicals, advanced materials, and integrated biorefineries. Fractionation and depolymerization methods yield liquid repositories of promising aromatic monomers and lignin oligomers (LO) that retain many of the structural components found in the native material. However, analyzing this complex mixture is challenging due to the wide range of molecular sizes and heterogeneous chemical structure, which makes their structural elucidation a critical obstacle - unlocking the full potential of lignin hinges upon developing appropriate standards and analytical methods to address existing knowledge gaps. This review provides a comprehensive examination of current analytical techniques for elucidating the chemical structure of lignin oligomers, exploring synthesis methods, molecular structures, and their advantages and limitations. Built upon these findings, opportunities for synergy between synthetic oligomers and lignin utilization can be revealed, such as bioactive compound production and biorefinery integration. Moreover, we underscore the need for standardized analytical methods to facilitate the design of lignin oligomer standards and their diverse applications.