In recent years, the potential of lignins as a resource for material-based applications has been highlighted in many scientific and nonscientific publications. But still, to date, a lack of detailed structural knowledge about this ultracomplex biopolymer undermines its great potential. The chemical complexity of lignin demands a combination of different, powerful analytical methods, in order to obtain these necessary information. In this paper, we demonstrate a multispectroscopic approach using liquid-state and solid-state Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and nuclear magnetic resonance (NMR) spectroscopy to characterize a fractionated LignoBoost lignin. Individual FT-ICR-MS, tandem MS, and NMR results helped to determine relevant information about the different lignin fractions, such as molecular weight distributions, oligomer sizes, linkage types, and presence of specific functional groups. In addition, a hetero spectroscopic correlation approach was applied to chemometrically combine MS, MS/MS, and NMR data sets. From these correlation analyses, it became obvious that a combination of tandem MS and NMR data sets gives the opportunity to comprehensively study and describe the general structure of complex biopolymer samples. Compound-specific structural information are obtainable, if this correlation approach is extended to 1D-MS and NMR data, as specific functional groups or linkages are verifiable for a defined molecular formula. This enables structural characterization of individual lignin compounds without the necessity for tandem MS experiments. Hence, these correlation results significantly improve the depth of information of each individual analysis and will hopefully help to structurally elucidate entire lignin structures in the near future.