<p>D-<i>π</i> hybridization is a key structural feature that may significantly affect the intrinsic electronic properties of metallopolymers. Herein, we present the electrosynthesis and memristive properties of metallopolymers using the distinct d-<i>π</i> hybridization monomers R₁ and R₂. R₁ (Ru^II-(tpz)Cl₂) features tetradentate ligands (tpz, 6,6′-di(1<i>H</i>-pyrazol-1-yl)-2,2′-bipyridine) enforcing quasi-octahedral geometry; R₂ (Ru^II-(bpp)₂) incorporates tridentate ligands (bpp, 2,6-di(1<i>H</i>-pyrazol-1-yl)pyridine) inducing pronounced geometric distortion. The planar ligand (tpz) in R₁ facilitates ordered molecular assembly through high conformational rigidity and extensive <i>π</i>-<i>π</i> stacking, resulting in increased molecular densities and enhanced morphological uniformity compared to R₂ metallopolymers. Due to pyrazole’s weaker <i>π</i>-acceptance and stronger <i>σ</i>-donation compared to pyridine, R₁ exhibits a 119 nm red-shift in metal-to-ligand charge transfer (MLCT) band and a 30 mV anodic shift in Ru^+2/+3 redox potential relative to R₂. Coupled with a reduced HOMO–LUMO gap, the uniform and ordered structure leads to a lower conductance decay constant in R₁. Additionally, R₂ metallopolymers exhibit superior memristive performance (characterized by lower switching voltage and higher switching ratio) <i>via</i> redox-induced aromatic transitions in axial ligands enhancing electronic delocalization. This work compares two metallopolymers with different ligand geometries, revealing how this difference leads to distinct charge transport and memristive behaviors.</p>