Abstract Lithium (Li) is a critical element driving the transition toward a decarbonized environment by enabling sustainable energy storage and use in modern infrastructure. Over the past decades, the widespread exploitation of electronic devices and electric vehicles (EVs) has significantly driven global demand for Li. Although Li is primarily extracted from ore deposits, the increasing depletion of mineral resources has shifted focus toward other sources, such as seawater and salt lake brines. Several methods have been employed to recover Li from saline water (brine and seawater) at laboratory and pilot scales, which can be categorized into conventional and direct lithium extraction (DLE) approaches. Conventionally, the lime‐soda evaporation method has been widely applied for extracting Li from brine; however, this approach limits brine with low Mg/Li ratios and low efficiency. On the other hand, this review focuses on the DLE approaches, particularly electrochemical techniques, via electrolysis, electrodialysis, and capacitive dialysis for Li recovery. The advancements in the synthesis of working electrode materials (i.e., lithium iron phosphate [LiFePO 4 ]), electrode modifications, and membrane modifications for enhancing Li recovery and selectivity are highlighted. Current challenges and future perspectives, particularly on scaling these innovations from bench‐scale to industrial applications, and the technical challenges relating to the process scale of electrochemical extraction approaches are discussed, together with future research directions. In short, this review provides useful insights into the potential of electrochemical approaches as sustainable, effective, and cost‐efficient processes that facilitate the discovery of novel approaches to satisfy the growing worldwide need for Li.