Electrochemical alcohol oxidation, the alternate of oxygen evolution reaction, has been recognized as an effective way to produce value-added chemicals coupled with H₂ production. However, the current researches still suffer from the low reaction rate and Faradaic efficiency (FE) that limits the overall efficiency. Herein, we report a ligand intercalation strategy to enhance the current density of alcohol electrooxidation by intercalating sodium dodecyl sulfonate (SDS) in the interlayer of Co(OH)₂ catalyst (Co(OH)₂-SDS). For instance, the Co(OH)₂-SDS shows obviously enhanced current density for glycerol electrooxidation than that of pure Co(OH)₂. The corresponding glycerol conversion rate and H₂ production rate reach 0.35 mmol·cm⁻²·h⁻¹ and 9.1 mL·cm⁻²·h⁻¹ at 1.42 V vs. reversible hydrogen electrode, which are 2.2- and 1.9-fold higher than that of Co(OH)₂. The yield of formate reaches 86.6% with selectivity of 95.3% at high glycerol conversion of 95.1% (with FE of 83.3% for glycerol oxidation). The Co(OH)₂-SDS is demonstrated efficient for different alcohols with enhanced performance. We confirmed that the intercalation of SDS in Co(OH)₂ can promote the generation and exposure of CoOOH reactive sites, and also facilitate the adsorption of alcohol, thus enabling high reaction rate.