The purity of sodium carbonate solution is critical for membrane electrolysis to efficiently produce sodium hydroxide and bicarbonate. This study reports electrochemically enhanced adsorption of aluminum from sodium carbonate solution by activated carbon fibers. The parameters examined included: bias potential, pH, aluminum concentration, and sodium carbonate concentration. The electrosorption process followed the Lagergren first-order kinetics and the experimental results were fitted to the Langmuir and Freundlich isotherms. The results demonstrate that the adsorption can be well-described by the Langmuir isotherms and occurs mainly in the monolayer.