The novel pyridine oxime-based complexing agents 2-pyridinecarboxaldehyde oxime, 2-acetylpyridine ketoxime and 2-pyridine amidoxime were synthesized for alkaline Zn-Ni alloy electrodeposition, outperforming conventional citrate/TEPA systems in corrosion resistance and microstructural control. The N,O-bidentate chelation mechanism governs metal ion reduction kinetics via diffusion-limited pathways, enabling γ-phase Ni₅Zn₂₁ intermetallic formation and nanocrystalline refinement. Electrochemical and microstructural analyses demonstrate suppressed random nucleation and hydrogen evolution side reactions, leading to enhanced charge transfer resistance and reduced corrosion current density. Notably, 2-pyridine amidoxime achieves ultrasmooth surfaces through defect-free nanocluster growth, while 2-pyridinecarboxaldehyde oxime maximizes γ-phase crystallinity. The synergy between grain boundary density and surface integrity establishes a dual protection mechanism combining barrier layer formation and active dissolution suppression. This work advances microstructure engineering via coordination chemistry, offering a breakthrough over traditional zincate electroplating for high-performance anti-corrosion coatings.