The rotational dynamics of 1-alkyl-3-methylimidazolium-based ionic liquids has been investigated by monitoring their inherent fluorescence with the intent to unravel the characteristics of the emitting species. For this purpose, temperature dependent luorescence anisotropies of 1-alkyl-3-methylimidazolium (alkyl = ethyl and hexyl) ionic liquids with anions such as tris pentafluoroethyl) trifluorophosphate ([FAP]), bis(trifluoromethylsulfonyl)imide ([Tf₂N]), tetrafluoroborate ([BF₄]), and hexafluorophosphate ([PF6]) have been measured. It has been observed that the reorientation times (τ_r) of the ionic liquids with an ethyl chain scale linearly with viscosity and were found to be independent of the nature of the anion. The experimentally measured τ_r values are a factor of 3 longer than the ones calculated for 1- ethyl-3-methylimidazolium cation using the Stokes−Einstein−Debye (SED) hydrodynamic theory with stick boundary condition, which suggests that the emitting species is not the imidazolium moiety but some kind of associated species. The reorientation times of ionic liquids with a hexyl chain, in contrast, follow the trend τ_r ^[FAP] > τ_r ^[Tf₂N] = τ_r ^[BF₄] > τ_r ^[PF₆] at a given viscosity (η) and temperature (T). The ability of the ionic liquids with longer alkyl chains to form the organized structure appears to be responsible for the observed behavior considering  the fact that significant deviations from linearity have been noticed in the τr versus η/T plots for strongly associating anions [BF₄] and [PF₆], especially at ambient temperatures.