Sequential investigation of samples with several analytical technologies yields increased chemical information content and metabolome coverage. The LDI-MS/SIMS/CRM spatial correlation strategy is illustrated using tall perennial grass Miscanthus x giganteus cross sections. The LDI-MS grid (center top) is color-coded, corresponding to the intensity of m/z = 45 ions, obtained by laser desorption/ionization excitation spots on 100 μm centers. The yellow circle highlights the spot where high-resolution imaging was performed by both negative (m/z = 25, C2H-, top left) and positive (m/z = 43, C3H7+, bottom left) ion SIMS, as well as CRM, characterized by the cellulose band, 345–390 cm-1 (top right), and the lignin band, 1550–1650 cm-1 (bottom right). (Bottom center) Composite CRM image combining information from both cellulose (green) and lignin (yellow) bands. Reprinted with permission from []. Copyright 2010 American Chemical Society.