Buckwheat is a pseudocereal that has gained increasing interest of industry and consumers over the past decade. Little, however, is known about its dietary fiber composition and nonstarch polysaccharide structures. Analysis of the monosaccharide composition indicated large amounts of pectic polysaccharides in both insoluble and soluble fiber from buckwheat. Methylation analysis gave further insights into the structures of the polysaccharides. The corresponding partially methylated alditol acetates suggested only low amounts of galactans. Xyloglucans were the main hemicellulosic polysaccharides in the insoluble fiber fraction. Highly branched arabinans, exclusively substituted at position O3, were of higher abundance. These results were confirmed by screening endo‐arabinanase and endo‐galactanase liberated oligosaccharides with high‐performance anion‐exchange chromatography with pulsed amperometric detection and LC‐MS2. Application of this method also demonstrated highly branched arabinan areas within the pectic polysaccharides. Only low amounts of fiber associated hydroxycinnamic acids and diferulic acids were liberated by alkaline treatment, and no evidence was found for their attachment to polysaccharides, suggesting only a minor impact of these structural elements on fiber structures in dehulled buckwheat seeds.