In this study, high-performance modified biochar/alginate composite bead (MCB/ALG) adsorbents were prepared from recycled agricultural waste corncobs by a high-temperature pyrolysis and KOH/FeCl3 activation process. The prepared MCB/ALG beads were tested for the adsorption of methylene blue (MB) dye from wastewater. A variety of analytical methods, such as SEM, BET, FTIR and XRD, were used to investigate the structure and properties of the as-prepared adsorbents. The effects of solution pH, time, initial MB concentration and adsorption temperature on the adsorption performance of MCB/ALG beads were discussed in detail. The results showed that the adsorption equilibrium of MB dye was consistent with the Langmuir isothermal model and the pseudo-second-order kinetic model. The maximum adsorption capacity of MCB/ALG−1 could reach 1373.49 mg/g at 303 K. The thermodynamic studies implied endothermic and spontaneous properties of the adsorption system. This high adsorption performance of MCB/ALG was mainly attributed to pore filling, hydrogen bonding and electrostatic interactions. The regeneration experiments showed that the removal rate of MB could still reach 85% even after five cycles of experiments, indicating that MCB/ALG had good reusability and stability. These results suggested that a win-win strategy of applying agricultural waste to water remediation was feasible.