The development of single-ion solid polymer electrolytes with high ion conductivity holds the key to the realization of safe, long-lasting, high-energy batteries. Here we introduce the use of core-shell nanostructured polyanionic particles, composed of polyanion asymmetric miktoarm stars with a large number of glassy polystyrene-based polyanion arms that complement longer poly(ethylene oxide), PEO, arms, as additives to low molecular weight, liquid PEO. Due to the proposed macromolecular design approach, the polyanion particles are well dispersed for wt % ≤ 55 that enables the formation of a nanostructured single-ion electrolyte with highly interconnected channels composed of liquid PEO that promotes fast ion transport. Noticeably, while the ion conductivity remains fairly unaffected and close to 10-5 S/cm at room temperature with nanoparticle loading, the shear modulus monotonically increases by several order of magnitudes indicating a very strong decoupling between the antagonistic properties of mechanical modulus and ion conductivity.