Lignin is a complex macromolecule that possesses a high potential for various material-based applications in the near future. In order to retrieve this potential, more detailed knowledge about the structural composition of lignin is required. One possible way to solve this problem is the application of ultrahigh resolving analysis methods such as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). In most studies from the last years, mainly dissolved lignin compounds, which only represent a fraction of the overall sample, were utilized for MS investigations. In this study, both soluble and insoluble lignin compounds of three different lignins (Kraft and Lignoboost lignins) were analyzed by electrospray ionization (ESI) and graphite-assisted laser desorption/ionization (GALDI) in combination with FT-ICR-MS. The different MS analyses demonstrated that ESI- and liquid GALDI-MS analyses can assist in the characterization of lignin molecules, which possess a high solubility in solvents of high polarity. In contrast, solid GALDI-MS provides insights about less polar molecules that have a low solubility in most solvents. Due to this higher molecular range of analyzable lignin compounds, the novel results will, hopefully, help to improve our understanding of the lignin structure and to utilize this interesting biopolymer in a more expedient and efficient way in the future.