Segregation of polar and nonpolar domains in ionic liquids for which either the cation or anion is responsible for inducing nonpolar domains is well understood. On the other hand, information regarding the nanoscale heterogeneities originating due to the presence of nonpolar content on both the ions is rudimentary at this point. The present contribution is aimed at addressing, this question and focuses on a molecular dynamics simulation study to probe nanoscale structural and aggregation features of the 1-n-alkyl-3-methylimidazolium [C(n)mim] octylsulfate [C8SO4 ] ionic liquid homologous series (n = 2, 4, 6, 8, 10, and 12). The objective of this work is to determine the effect of increasing alkyl chain length in the cation on nonpolar domain formation, especially when the alkyl chain lengths from both the ions participate in defining such domains. The results indicate that all-the ionic liquids form nonpolar domains, morphology of which gradually changes from globular, sponge-like to layer-Ike structure with increase in the cationic alkyl chain length. The length of the nonpolar domains calculated from the total structure factor for [C(10)mim] [C8SO4] is considerably higher than that reported for other imidazolium-based ionic liquid containing smaller anions. The structure factor for [C(12)mim][C8SO4] ionic liquid contains multiple intermediate peaks separating the charge alternation peak and pre-peak, which points to nonpolar domains of varying lengths, an observation that remains to be validated. Analysis of the heterogeneous order parameters and orientational correlation functions of the alkyl chains further-suggests an increase in the spatial heterogeneity and long-range order along the homologous series. The origin of rich diversity of Structures obtained by introducing nonpolar content on both the ions is discussed.