In the recent past, nonaqueous microemulsions containing ionic liquids (ILs) have been utilized for performing chemical reactions, preparation of nanomaterials, and synthesis of nanostructured polymers and in drug delivery systems. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions. In our earlier publication (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N.J. Phys. Chem. B 2012, 116, 2850-2855), we presented for the first time the possibility of creating huge number of IL-in-oil microemulsions, just by replacing the inorganic cation, Na+, of NaAOT by any organic cation and using different ionic liquids as the polar core. In this manuscript we are interested in exploring the effect of temperature on such systems. We have characterized the phase diagram of the [Py][TF2N]/[C 4mim][AOT]/benzene ternary system at 298 K. We have shown that in the experimental temperature range employed in this study, the microemulsions remain stable and a slight decrease in the size of the microemulsions is observed with increasing temperature. We have reported the detailed study of solvent and rotational relaxation of coumarin 153 (C-153) in neat IL, N-methyl-N-propylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide ([Py][TF 2N]), and in [Py][TF2N]/[C4mim][AOT]/benzene microemulsions using steady state and picosecond time-resolved spectroscopy. We have monitored the effect of (i) varying the [Py][TF2N]/[C 4mim][AOT] molar ratio (R value) and (ii) temperature on solvent and rotational relaxation of C-153. The features observed in absorption and emission spectra clearly indicate that (i) the probe molecules reside at the polar interfacial region of the [Py][TF2N]/[C4mim][AOT]/benzene microemulsions and (ii) with increasing R value the probe molecules move toward the polar IL-pool of the microemulsion. We have shown that the increase in solvation time on going from neat [Py][TF2N] to [Py][TF 2N]-containing microemulsions is very small compared to the increase in solvation time on going from pure water to water-containing microemulsions. The average solvation time decreases with increasing R values at 298 K, but it shows only a small R dependence compared to microemulsions containing solvents capable of forming hydrogen bonds. We have also shown that the temperature has substantial effect on the solvent and rotational relaxation of C-153 in neat [Py][TF2N] compared to that of [Py][TF2N]/[C 4mim][AOT]/benzene microemulsions at R = 0.69.