Barium ion cross-linked alginate beads have shown great affinity to toxic hexavalent chromium ions in aqueous solution, in contrast to the traditionally used calcium alginate beads. Our adsorption experiments were carried out by the batch contact method. The optimal pH for removal was found to be pH 4. The equilibrium was established in 4 h, and the removal efficiency of chromium (VI) was found to be 95%. The adsorption data were applied to Langmuir, Freundlich, Dubinin–Redushkevich (D–R), and Temkin isotherm equations. Both Langmuir and Freundlich isotherm constants indicated a favorable adsorption. The value of mean sorption energy calculated from D–R isoterm indicates that the adsorption is essentially physical. The high maximum chromium (VI) adsorption capacity was determined from the Langmuir isotherm as 36.5 mg/g dry alginate beads. The chromium (VI) adsorption data were analyzed using several kinetic models such as the pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models, and the rate constants were quantified. Our study suggests that barium alginate beads can be used as cost-effective and efficient adsorbents for the removal of chromium (VI) from contaminated waters.