Understanding the molecular-level organization of anions and cations in a mixture of different ionic liquids (ILs) is challenging, but it can be very important for designing solvents and IL-based membrane materials. Here, we perform all-atom molecular dynamics (MD) simulations to understand the intermolecular interactions and structuring of both neat and mixed IL compositions containing 1-benzyl-3-methylimidazolium [ZMIM+], 1-butyl-3-methylimidazolium [BMIM+], bistriflimide [Tf2N−], and tetrafluoroborate [BF4−]. We observe very strong underlying molecular-level migrations in these mixtures, and this tends to mainly involve the anion species. As compared to the systems with a single anion, the mixed anions lead to large increases/decreases in the radial distribution function peak heights, whereas the cation mixing is relatively benign. The [BF4−] anions have a strong tendency to displace the [Tf2N−] anions in the mixtures, and this is seen with respect to both [BMIM+] and [ZMIM+]. © 2020 Elsevier Ltd