In this communication, we explore solute–solvent and ion–ion interactions within binary ionic liquid mixtures. From the perspective of several solvatochromic reporter probes capable of a range of interactions, we have investigated the influence of mixture composition on the polarity, dielectric, hydrogen bonding interactions, and microfluidity within mixtures afforded by the ionic liquids 1-butyl-3-methylimidazolium bis(triflyl)imide, 1-ethyl-3-methylimidazolium bis(triflyl)imide, and 1-butyl-3-methylimidazolium hexafluorophosphate. Our results underscore the prevalence of hydrogen bond donor and competitive anion coordination effects, suggesting the possible use of such mixtures in the design and optimization of advanced media for separations or chemical processing.