The structural organization in selected room temperature ionic liquids, namely (a) butyl-, (b) hexyl- and (c) octyl-3-methylimidazolium hexafluorophosphate, is investigated by means of X-ray diffraction. We find novel experimental evidences of the existence of a high degree of intermediate range order that is associated to nanoscale segregation of the alkyl chains into the charged matrix. The size of these structural heterogeneities depends linearly from the alkyl chain length. A similar behaviour had been observed in other systems, such as normal alcohols. The slope of such dependence provides hints on the nature of the structural organization of these segregated domains. (c) 2008 Elsevier B. V. All rights reserved.