The structural organization of chitosan hydrogel beads (CSBs) formed by various anionic surfactants, sodium dodecyl sulfate (SDS), sodium decyl sulfate (DS), dodecyl benzenesulfonic acid sodium salt (SDBS), and dioctyl sulfosuccinate sodium salt (DSS), and their applications as adsorbents for environmental purifications were investigated using Congo red (CR) as a model dye. The adsorption capacities of CSB as a function of surfactant concentration revealed that CSBs formed by 5g/L anionic surfactant were the most effective for CR adsorption. The structure of CSBs and their adsorption capacities for CR depend on the nature of anionic surfactants. The maximum adsorption capacities of CSBSDS, CSBDS, CSBSDBS, and CSBDSS obtained from the Langmuir isotherm model were 186.02, 209.28, 207.25, and 113.83mg/g, respectively, indicating that CSBDS was the best adsorbent for CR.