The optimization of ionic conductivity and lithium-ion battery stability can be achieved by independently tuning the ion transport and mechanical robustness of block polymer (BP) electrolytes. However, the ionic conductivity of BP electrolytes is inherently limited by the covalent attachment of the ionically conductive block to the mechanically robust block, among other factors. Herein, the BP electrolyte polystyrene-block-poly(oligo-oxyethylene methacrylate) [PS-bPOEM] was blended with POEM homopolymers of varying molecular weights. The incorporation of a higher molecular weight homopolymer additive (alpha > 1 state) promoted a "dry brush-like" homopolymer distribution within the BP self-assembly and led to higher lithium salt concentrations in the more mobile homopolymer-rich region, increasing overall ionic conductivity relative to the "wet brush-like" (alpha < 1 state) and unblended composites, where a is the molecular weight ratio between the POEM homopolymer and the POEM block in the copolymer. Neutron and X-ray reflectometry (NR and XRR, respectively) provided additional details on the lithium salt and polymer distributions. From XRR, the alpha > 1 blends showed increased interfacial widths in comparison to their BP (unblended) or alpha < 1 counterparts because of the more central distribution of the homopolymer. This result, paired with NR data that suggested even salt concentrations across the POEM domains, implied that there was a higher salt concentration in the homopolymer POEM-rich regions in the dry brush blend than in the wet brush blend. Furthermore, using Li-7 solid-state nuclear magnetic resonance spectroscopy, we found a temperature corresponding to a transition in lithium mobility (T-Li (mobility)) that was a function of blend type. T-Li (mobility) was found to be 39 degrees C above T-g in all cases. Interestingly, the ionic conductivity of the blended BPs was highest in the alpha > 1 composites, even though these composites had higher T(g)s than the alpha < 1 composites, demonstrating that homopolymer-rich conducting pathways formed in the alpha > 1 assemblies had a larger influence on conductivity than the greater lithium ion mobility in the alpha < 1 blends.