X-ray scattering and molecular dynamics simulations have been carried out to investigate structural differences and similarities in the condensed phase between pyrrolidinium-based ionic liquids paired with the bis(trifluoromethylsulfonyl)amide (NTf2-) anion where the cationic tail is linear, branched, or cyclic. This is important in light of the charge and polarity type alternations that have recently been shown to be present in the case of liquids with cations of moderately long linear tails. For this study, we have chosen to use the 1-alkyl-1-methylpyrrolidinium, Pyrri(1,n)(+) with n = 5 or 7, as systems with linear tails, 1-(2ethylhexyl)-1-methylpyrrolidinium, Pyrr(1,Ethx)(+), as a system with a branched tail, and 1-(cyclohexylmethyl)-1-methylpyrrolidinium, Pyrr(1,Ethx)(+), as a system with a cyclic tail. We put these results into context by comparing these data with recently published results for the Pyrr(1,n)(+)/NTf2- ionic liquids with n = 4, 6, 8, and 10.(1,2) General methods for interpreting the structure function S(q) in terms of q-dependent natural partitionings are described. This allows for an in-depth analysis of the scattering data based on molecular dynamics (MD) trajectories that highlight the effect of modifying the cationic tail.