A new series of polysiloxane-based single-ion conductors was prepared. These contain solvating oligoether sidechains and covalently linked aluminosilicate or alkoxy/siloxy-aluminate anions attached to the polysiloxane backbone. Of these two systems, the polymers containing aluminosilicate [(SiO)4Al]− anions show higher room temperature conductivities (10−6 S/cm) than those with alkoxy/siloxyaluminate [(SiO)2(CH2O)2A1]− anions (10−7 S/cm). The incorporation of longer covalent tethers between the alkoxy/siloxyaluminate anion and the polymer backbone results in enhanced room temperature conductivities at high ion loadings. Differential scanning calorimetry data provide a rationale for the high conductivity.