In the present study, an ionic liquid (IL), known as green solvent, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4) with four carbons in the hydrophobic chain (C-4) has been used as an additive to modify the self-assembled aggregates of an anionic surfactant sodium dodecyl sulfate (SDS) and then the evolution of the liquid crystalline phases has been investigated. Small angle synchrotron x-ray diffraction study has revealed an unprecedented phase sequence where a hexagonal phase (HI) of direct cylindrical micelles is observed to evolve to another hexagonal phase (HII) of, again, direct cylindrical micelles with a lamellar phase (Lα) as the intermediate. The rheological data and the theoretical calculations have confirmed the phases. To understand such a phase behaviour of the system, the work is extended by considering the ionic liquids with the same head group but of shorter (C-2) and longer (C-10) hydrocarbon chains compared to BMIM-BF4. While the shorter chain IL causes the hexagonal phase to form rectangular (R) phase, the longer chain is observed to induce the lamellar phase (Lα). The molecular mechanism of appearance of such different phases has been discussed. © 2019, © 2019 Informa UK Limited, trading as Taylor & Francis Group.