• Cationic benzyltriethylammonium chloride enables high (002)-textured Zn via selective adsorption, outperforming prior additives.
• In situ homogenization converts commercial Zn foil into highly (002)-textured Zn anodes without pretreatments.
• Cl−-induced pitting corrosion mechanism uncovered, leading to a breakthrough in performance limits of Zn anodes.
• TEBA+-modified Zn||VO2 full cell demonstrates high specific capacity and robust cycle stability at 10.0 A g−1.