Aqueous Zn batteries are subject to uncontrollable dendrite growth and water-induced parasitic side reactions, resulting in poor Zn²⁺ kinetics and limited lifespan. Herein, a self-consistent ultrathin multifunctional layer by integrating hydrophobic siloxane-based block and zincophilic diphosphate-building block into molecular skeletons on Zn foils (MTSi-Hedp-Zn) is proposed by a scalable and low-cost dip-coating technique. Experimental results combined with theoretical calculation (DFT) and COMSOL Simulations reveal that abundant O-Si-CH₃ groups as hydrophobic block in the top of molecular skeletons is the contributing factor in precluding solvated H₂O corrosion. Zincophilic Pdouble bondO bonds on organic phosphate block in the backbone work as attraction area for fast Zn²⁺ adsorption and transport kinetics. Simultaneously, such a combination enables surface-preferred (002) crystal planes on Zn metal, synergistically homogenizing the electric field at the interface and achieving preferentially flat growth without dendrites and side reactions. Accordingly, the MTSi-Hedp-Zn electrode exhibits an extended lifespan of over 2000 h and a much low voltage polarization of ~24.3 and 67.5 mV at 1 and 10 mA cm⁻², respectively. Practical full cells coupled with commercial cathodes (CNT/MnO₂ and V₂O₅) both perform much better capacity retention than the bare Zn case. The proposed hydrophobic-zincophilic interface by silane-organic phosphoric acid provides a significant construction tactic for designing dendrite-free and corrosion-free Zn electrodes and beyond.