Cell wall polysaccharides (CWPS), which are usually covalently bound to the peptidoglycan and are closely associated with the cell wall, are considered as ubiquitous components of the cell envelope of gram-positive bacteria and play an important role as mediators of bacterial interactions with the environment. Here, we describe a simple method for purifying CWPS by extraction of bacterial cells with consecutive acid treatments. Purified CWPS are obtained by gel-filtration chromatography following treatment with HF. We also provide the methodology to easily assess the integrity of CWPS using high-resolution magic-angle spinning (HR-MAS) NMR.