The present study developed novel functionalized corncobs introducing brushes with dense and active carboxyl groups (–COOH), named MC-g-PAA, for the highly efficient adsorption of Pb2+ from aqueous solutions. MC-g-PAA were synthesized via atom transfer radical polymerization (ATRP) and characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The amount of Pb2+ adsorbed on MC-g-PAA by hydrolysis with t-BuOK was 2.28 times greater than that with NaOH, attributed to the larger steric effect of t-BuOK, which reduced the hydrolysis of the bromo-ester groups. The influence of different parameters including the solid/liquid ratio, working solution pH, sorption temperature, and initial concentration and sorption time on the adsorption of Pb2+ were investigated in detail in batch experiments. Thermodynamic studies have shown that the adsorption process was spontaneous, endothermic, and accompanied by an increase in randomness. A better fit for the isotherm data was obtained using the Langmuir model than for the other four models and the maximum amount (qmax) of Pb2+ adsorbed on MC-g-PAA was 342.47 mg/g, which is 21.11 times greater when compared with that of pristine corncobs (16.22 mg/g). The adsorption of Pb2+ on MC-g-PAA was very fast and followed the pseudo-second-order kinetic equation with a correlation coefficient of 0.99999. This monolayer adsorption process was dominated by chemical adsorption, and may proceed according to complexation and electrostatic interactions between Pb2+ and the carboxylate groups. This study indicated that MC-g-PAA could be successfully used as an adsorbent for the removal of Pb2+ from aqueous solutions due to its excellent efficiency.