The room-temperature ionic liquid [C3mpyr][Tf2N] and its binary mixtures with methanol and acetonitrile provide microenvironments of varying viscosity, polarity, and hydrogen-bonding ability. The present work highlights their effects on the photophysics and rotational dynamics of a potent excited-state intramolecular double-proton-transfer (ESIDPT) probe, 2,2′-bipyridine-3,3′-diol [BP(OH)2]. The rotational diffusion of the proton-transferred diketo (DK) tautomer in [C 3mpyr][Tf2N] ionic liquid was analyzed for the first time from the experimentally obtained temperature-dependent fluorescence anisotropy data using Stokes-Einstein-Debye (SED) hydrodynamic theory and Gierer-Wirtz quasihydrodynamic theory (GW-QHT). It was found that the rotation of the DK tautomer in neat ionic liquid is governed solely by the viscosity of the medium, as the experimentally observed boundary-condition parameter, Cobs, was very close to the GW boundary-condition parameter (CGW). On the basis of photophysical studies of BP(OH)2 in IL-cosolvent binary mixtures, we suggest that methanol molecules form hydrogen bonds with the cationic counterpart of the DK tautomers, as evidenced by the greater extent of the decrease in the fluorescence lifetime of BP(OH)2 upon addition of methanol compared to acetonitrile. It is also possible for the methanol molecules to form hydrogen bonds with the constituents of the RTIL, which is supported by the lesser extent of the decrease in the viscosity of the medium upon addition of methanol, leading to a less effective decrease in the rotational relaxation time compared to that observed upon acetonitrile addition.