We have studied ion transport in electrolytes created by blending two different polymers and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The polymers covered in this study are poly(ethylene oxide) (PEO), poly(1,3,6-trioxocane) (P(2EO-MO)), and poly(1,3-dioxolane) (P(EO-MO)). Ion transport is quantified by the product κρ₊ which is defined as the efficacy of the electrolytes, where κ is conductivity and ρ₊ is the current fraction determined by the Bruce–Vincent method. Polymer blends can be either one-phase or macrophase-separated. We used small-angle neutron scattering (SANS) to distinguish between these two possibilities. The random phase approximation (RPA) was used to interpret SANS data from one-phase blends. The effect of added salt on polymer blend thermodynamics is quantified by an effective Flory–Huggins interaction parameter. All polymer blends were one-phase in the absence of salt. Adding salt in small concentrations results in macrophase separation in all cases. One-phase systems were observed in the PEO/P(EO-MO)/LiTFSI blends at high salt concentrations. In most of the polymer blend electrolytes, the measured κρ₊ was either lower than or comparable to that of the homopolymer electrolytes. An exception to this was one-phase PEO/P(EO-MO)/LiTFSI blends electrolytes at high salt concentrations.