Generally, surfactants (or amphiphiles) are believed to be necessary components of microemulsions. However, it has been demonstrated that, in the absence of traditional surfactants, microemulsions can also form from a ternary system of two immiscible fluids (i.e., oil and water phases) and an amphi-solvent, but the current understanding of such surfactant-free microemulsions (SFMEs) is very limited. Herein, we report an SFME consisting of the hydrophobic ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), the protic IL propylamine nitrate (PAN), and water, in which bmimPF6 and PAN are used as the oil phase and the amphi-solvent, respectively. The microstructures and structural transitions of the SFME were investigated using cyclic voltammetry, fluorescence spectroscopy, and ultraviolet-visible spectroscopy. The SFME exhibited water-in-bmimPF6 (W/IL), bicontinuous (BC), and bmimPF6-in-water (IL/W) microstructures, depending on the composition of the ternary system, similar to the case of traditional surfactant-based microemulsions (SBMEs). The three kinds of microstructures were confirmed by cryogenic transmission electron microscopy (cryo-TEM) observations. To the best of our knowledge, this is the first report on SFMEs composed of two ILs as components, especially where one is used as the amphi-solvent.