Thick electrodes greatly enhance lithium extraction capacity. However, with the increase of active substances loading, the traditional thick electrodes are more hydrophobic, severely limiting the utilization of active substances. Hence, a sulfonation process to functionalize thick electrodes was applied to enhance their wettability (~45 mg·cm⁻¹) in brine. Experimental and theoretical results show that the lithium extraction capacity of thick electrodes can be significantly improved by enhancing the electrodes hydrophilicity. At 0.8 V, the S-PVDF electrode's capacity for lithium extraction in simulated brine (41.72 mg·g⁻¹) significantly surpassed the PVDF electrode (35.72 mg·g⁻¹), and it also performed well in actual brine (28.8 mg·g⁻¹). The Mg²⁺/Li⁺ ratio in actual brine dropped from 65 to 0.37, achieving effective magnesia‑lithium separation. This method offers a novel approach to developing high-efficiency lithium extraction thick electrodes.