Electrochemical deionization is regarded as one of the promising water treatment technologies. Here, CoAl‐layered metal oxide nanosheets intercalated by sodium dodecyl sulfate (SDS) with an enhanced interlayer spacing from 0.76 to 1.33 nm are synthesized and used as an anode. The enlarged interlayer spacing provides an enhanced ion‐diffusion channel and improves the utilization of the interlayer electroactive sites, while heat treatment, transferring layered double hydroxides to layered metal oxides (LMOs), offers additional active oxidation reaction sites to facilitate the electro‐sorption rate, contributing to the high salt adsorption capacity (31.78 mg g−1) and average salt adsorption rate (3.75 mg g−1 min−1) at 1.2 V in 500 mg L−1 NaCl solution. In addition, the excellent long‐term cycling stability (92.9%) after 40 cycles proves the strong electronic interaction between SDS and the host layer, which is validated by density functional theory calculations later on. Moreover, the electro‐sorption mechanism of LMOs that originated from the reconstruction of the layered structure based on the “memory effect” is revealed according to the X‐ray photoelectron spectroscopy peak shifts of Co element. This strategy of expanding the interlayer spacing combined with heat treatment makes LMOs a competitive candidate for electrochemical water deionization.