To solve the water pollution problem caused by methylene blue (MB), areca residue biochar (ARB) was prepared by pyrolysis at 600 °C, and modified areca residue biochar (M-ARB) was obtained by modifying ARB with 1.5 mol/L NaOH, and they were utilized to adsorb and eliminate MB from water. The structural characteristics of ARB and M-ARB were examined, and the main influencing factors and adsorption mechanism of MB adsorption process were investigated. The outcomes demonstrated an increase in M-ARB’s specific surface area and total pore volume of 66.67% and 79.61%, respectively, compared with ARB, and the pore structure was more abundant, and the content of oxygen element was also significantly increased. When the reaction temperature was 25 °C, starting pH of the mixture was 10, the initial MB concentration was 50 mg/L, the ARB and M-ARB dosages were 0.07 g/L and 0.04 g/L, respectively, the adsorption equilibrium was achieved at about 210 min, and the elimination rate for MB exceeded 94%. The adsorption behaviors of ARB and M-ARB on MB were more in line with the Langmuir isotherm model (R2 > 0.95) and the quasi-secondary kinetic model (R2 > 0.97), which was characterized by single-molecule layer chemisorption. The highest amount of MB that may theoretically be absorbed by M-ARB in water ranging from 136.81 to 152.72 mg/g was 74.99–76.59% higher than that of ARB. The adsorption process was a spontaneous heat absorption reaction driven by entropy increase, and the adsorption mechanism mainly involved electrostatic gravitational force, pore filling, hydrogen bonding, and π–π bonding, which was a complex process containing multiple mechanisms of action. NaOH modification can make the ARB have more perfect surface properties and more functional group structures that can participate in the adsorption reaction, which can be used as an advantageous adsorption material for MB removal in water.