Cassava (Manihot esculenta Crantz) is considered the third most important source of calories in tropical regions. Up to one third of cassava harvested worldwide is used in livestock production. The focus of this study was to characterize cassava cell wall structure to provide knowledge for a better application of cassava as an energy source in monogastric animal feed. A total of five cassava samples from different feed mills in South East Asia were investigated. On a dry matter basis, the cassava cell walls contained, on average, 640 mg g⁻¹ glucose, 140 mg g⁻¹ galactose, 50 mg g⁻¹ mannose, 80 mg g⁻¹ xylose, 60 mg g⁻¹ arabinose, 10 mg g⁻¹ fucose and 20 mg g⁻¹ rhamnose. RONOZYME VP (DSM Nutritional Products, Switzerland), a non-specific multicomponent non-starch polysaccharide (NSP) degrading enzyme (NSPase) product from Aspergillus aculeatus, solubilized about 10% of cassava NSP content during 4 h incubations at 40 °C and pH 5. There was notable solubilization of polymers containing uronic acids, galactose, arabinose and rhamnose. Immuno-microscopy imaging indicated the solubilization of pectin, galactan and xyloglucan polysaccharides from cassava cell wall. As a consequence, the starch granules became more available to exogenous α-amylase degradation.