In an attempt to understand the nature of interactions between organic solutes and room temperature ionic liquids, temperature-dependent rotational relaxation of two structurally similar nondipolar solutes-2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP)-has been examined in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim(+)][PF6-]). Even with the ionic liquid, where the cation and the anion are strongly associated, the solute DPP experiences specific interactions, which is evident from its reorientation times that are 50%-60% longer in relation to DMDPP. It has been noticed that the reorientation times of both the solutes are faster in [bmim(+)][PF6-] than in glycerol, which is also a strongly associated solvent and whose viscosity is similar to the ionic liquid. This observation has been explained by taking into consideration the relative sizes of the solvents. By comparing the ratios of the reorientation times of DPP to DMDPP, in [bmim(+)][PF6-] and glycerol, it has been deduced that the strengths of the interaction between DPP-[bmim(+)][PF6-] and DPP-glycerol are the same. (c) 2005 American Institute of Physics.