Adaptable redox-active materials hold great potential for electrochemically mediated separation processes via targeted molecular recognition and reduced energy requirements. This work presents molecularly tunable vinylferrocene metallopolymers (P(VFc-co-X)) with modifiable operating potentials, charge storage capacities, capacity retentions, and analyte affinities in various electrolyte environments based on the hydrophobicity of X. The styrene (St) co-monomer impedes hydrophobic anions from ferrocene access, providing P(VFc-co-St) with specific response capabilities for and greatly improved cyclabilities in hydrophilic anions. This adjustable electrochemical stability enables preferential chromium and rhenium oxyanion separation from both hydrophobic and hydrophilic electrolytes that significantly surpasses capacitive removal by an order of magnitude, with a robust perrhenate uptake capacity of 329 mg/g VFc competitive with established metal-organic framework physisorbents and 17-fold selectivity over 20-fold excess nitrate. Pairing P(VFc-co-X) with other solution-specific electroactive macromolecules such as the pH-dependent poly(hydroquinone) (PHQ) and the cesium-selective nickel hexacyanoferrate (NiHCF) generates dual-functionalized electrosorption cells. P(VFc-co-X)//PHQ offers optimizable energetics based on X and pH for a substantial 4.6-fold reduction from 0.21 to 0.04 kWh/mol rhenium in acidic versus near-neutral media, and P(VFc-co-St)//NiHCF facilitates simultaneous extraction of rhenium, chromium, and cesium ions. Proof-of-concept reversible perrhenate separation in flow further highlights such frameworks as promising approaches for next-generation water purification technologies.