The uncontrolled zinc electrodeposition in aqueous electrolytes, characterized by crystallographic randomness, remains a fundamental challenge due to dendritic growth and parasitic reactions. This work introduces a multifunctional organic–inorganic hybrid additive, magnesium bis(benzenesulfonyl)imide (Mg(BBI)₂), to precisely direct Zn deposition. The mechanistic studies reveal that the BBI⁻ anions preferentially adsorb onto the specific (101) and (100) Zn planes to block the nucleation sites of these two planes, thereby promoting a highly oriented deposition dominated by the (002) plane. Concurrently, the Mg²⁺ cations weaken the Zn²⁺-SO₄²⁻/H₂O interaction, serving as a long-term texture stabilizer for the single-textured electrodeposition. The tiny addition of Mg(BBI)₂ (0.02 M in 2 M ZnSO₄) achieves the Zn plating with a strikingly high (002) relative texture coefficient of 97.9% and superior corrosion resistance. Moreover, this hybrid molecular design represents a shift from the repurposing of existing molecules to purposefully functionalized synthesis, which endows durable high-zinc-utilization Zn||Zn symmetric cells and high-capacity full cells coupled with various cathodes, such as CaV₆O₁₆·2.7H₂O cathodes with high mass loading (16 and 22.6 mg·cm⁻²).