Dyeing effluent is one of the largest contributors to textile effluent and such colored wastewater has a seriously destructive impact on the environment. Adsorption can be a very effective treatment for decolorization of textile dyeing effluent, but current techniques employ adsorption chemistry that is not particularly environmentally friendly, such as the use of alum. In this study, natural polysaccharides were used as adsorbents for removal of dye molecules from effluent. The results showed that naturally cationic polysaccharides such as chitin and chitosan gave excellent levels of color removal, and this was attributed to a combination of electrostatic attraction, van der Waals forces, and hydrogen bonding. Nonionic galactomannans (locust bean gum, guar gum, cassia gum) were also highly effective in removing dye from effluent, whereas other nonionic polysaccharides, such as starch, were not effective. This was attributed to the structure of the polysaccharides and the relative degree of inter- and intramolecular interactions between separate polymer chains. The pendant galactose residues of galactomannans prevented strong interaction, allowing greater hydrogen bonding with dye; comparatively, starch has extensive chain interactions, and as such had limited potential for hydrogen bonding with the dye molecules at the temperature of application. In addition, hydrophobic interactions between the hydrophobic parts of the dye and the alpha-face of the pendant galactose residues may have contributed to the superior performance. Repulsion between anionic polysaccharides and the dye anions prevented any hydrogen bonding and as such pectin, carrageenans, and alginic acid were not effective in dye removal from effluent. The use of galactomannans derived from plants in this system presents a sustainable method of effluent treatment. The raw materials are derived from renewable plant sources and are available in tonnage quantities, the adsorption system itself is highly effective and does not involve any additional chemical input or treatment other than the use of the adsorbent, and the adsorption agents themselves are nontoxic and biodegradable.