Room-temperature ionic liquid (RTIL), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([P-13][Tf2N]), was substituted for polar water and formed nonaqueous microemulsions with benzene by the aid of nonionic surfactant TX-100. The phase behavior of the ternary system was investigated, and microregions of [P-13][Tf(2)zN]-in-benzene (IL/O), bicontinuous, and benzene-in-[P-13][Tf2N] (O/IL) were identified by traditional electrical conductivity measurements. Dynamic light scattering (DLS) revealed the formation of these IL microemulsions because with gradual increase of RTIL contents the droplet sizes of the microemulsions are also gradually increasing. Pulsed-field gradient spin echo NMR have been studied to measure the diffusion coefficients of neat [P-13][Tf2N] and [P-13][Tf2N] in microemulsions which indicate ionic liquid containing microemulsions is formed. Moreover, the dynamics of solvent relaxation have been investigated in [P-13][Tf2N]/TX100/benzene microemulsions using steady-state and time-resolved fluorescence spectroscopy using coumarin 153 (C-153) and coumarin 480 (C-480) fluorescence probe with variation of RTIL contents in microemulsions. For both of the probes with increasing amount of ionic liquids in microemulsions the relative contribution of the fast components increases and the slow components contribution decreases; therefore the average solvation time decreases.