Outlined in this chapter are strategies for the use of the analytical techniques of nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS) towards the elucidation of the structures of microbial wall glycans. Specifically, the determination of the structure of capsular polysaccharide, core oligosaccharide or O-antigen utilizing 1D, 1D selective and 2D homonuclear and heteronuclear NMR experiments and database resources is presented. Described is the application of high resolution magic angle spinning techniques for studying glycopolymer structures. MS sample derivatization strategies along with associated gas chromatography-mass spectrometry, sugar, linkage, and absolute configuration analyses are outlined. The use of fast atom bombardment, matrix-assisted laser desorption ionization and electrospray-mass spectrometry ionization techniques along with their associated mass analysers are presented for characterizing oligosaccharide, lipid A, lipooligosaccahride, ipopolysaccharide and capsular polysaccharide glycan structures.