Direct lithium extraction offers a more sustainable and flexible pathway as compared to the traditional evaporitic mining technology. Ensuring high lithium selectivity over other cations in the brine is a key challenge of this process. We investigate the possibility of harnessing H2TiO3 ion sieve as a material, which has been extensively studied in pH driven lithium capture, for selective electrochemical lithium extraction. Previous work has shown that selective lithium adsorption occurs in highly alkaline conditions, which enables the weakly acidic O-H group to dissociate and facilitates O-Li bond formation. In this work, we explore the possibility of achieving similar ion exchange effects through electrochemical pathways, which would eliminate the need for pH adjustment, thus minimizing the environmental impact induced by extreme pH conditions. We observed that the application of voltage bias (1.2V vs Ag/AgCl) could significantly enhance the surface concentration of lithium on the electrode, thus shifting the equilibrium towards a larger extent of lithium adsorption and can contribute to improving separation performance. On average, the applied voltage increases lithium adsorption uptake by more than six times compared to the physisorption control group. Superior selectivity for lithium was also achieved with separation factor over sodium and magnesium of 34.2 and 8.7, respectively. The advantage of this electrochemical separation process is that it does not rely on the pH of the feed brine solution, which could mitigate the necessity for acid and base addition during the lithium extraction process.