Cocoa bean shells (CBS), a by-product of the cocoa industry, from two cacao varieties and obtained after selected processing conditions (fermentation, drying, roasting) were characterized in terms of their chemical composition, where they were found to be a great source of carbohydrates, specifically dietary fiber, protein, ash, and polyphenols, namely quercetin, epicatechin, and catechin. Cell wall polysaccharides were isolated by alkaline extraction (0.5 M or 4 M KOH) and were found to be enriched primarily in pectic polysaccharides (80.6-86%) namely rhamnogalacturonan and arabinogalactan as well as hemi- cellulosic polysaccharides (13.9-19.4%). Overall, 0.5 M KOH polysaccharides were favored having provided a diverse profile of neutral sugars and uronic acids. When tested for the promotion of the growth of selected probiotic strains, CBS cell wall polysaccharides performed similarly or more than inulin and rhamnogalacturonan based on the prebiotic activity scores. The short-chain fatty acid profiles were characterized by high amounts of lactic acid, followed by acetic and propionic acid.