Dendrite-free Zn metal anodes with robust interface are highly desired for the practical application of aqueous zinc-metal based batteries (AZMBs), while their stability is hindered by the untoward [Zn(H$_2$O)$_6$]$^{2+}$ desolvation and succedent deposition with dissatisfactory kinetic barriers, especially under low-temperature environment. Herein, a self-cascade catalytic strategy on accelerating interfacial desolvation and optimizing diffusion is proposed by designing an atomically dispersed Bi within the deficient LaMnO$_{3.15}$ perovskite (SABi/U-LMO) layer on Zn anode. Theoretical calculations demonstrate that the d-band center and nonbonding state near the Fermi level of SABi/U-LMO alleviate the corrosion of H$_2$O and accelerate the dissociation of Zn$^{2+}$─H$_2$O bond by promoting the rapid filling of the empty 4s orbital of the Zn$^{2+}$, as revealed by electrochemical and spectroscopic results. Meanwhile, the redistribution of electric field with SABi/U-LMO realizes the delocalization and lateral growth of Zn atoms. Consequently, the cells with SABi/U-LMO render an impressive lifetime up to 5000 h at 1 mA cm$^{−2}$ as well as a high Coulombic efficiency of 99.59% over 2000 cycles under 0 °C. Full cell also stabilizes the capacity retention of ∼100% after 900 cycles at 1 A g$^{−1}$ under −20 °C, verifying the feasibility of self-cascade catalysis in realizing high-performance AZMBs.