In an attempt to understand the role of interfacial friction on solute rotation, fluorescence anisotropy decays of a cationic solute, rhodamine 110, have been measured in polymorphic environments of a triblock copolymer, (PEO)(20)-(PPO)(70)-(PEO)(20) (P123) (PEO = poly(ethylene oxide), PPO = poly(propylene oxide)). It has been noticed that even though rhodamine 110 is located in the interfacial region of the micelles, sol-gel transition does not significantly influence its rotation. Micelle-micelle entanglement, which is responsible for gelation, persists even in the micellar solution phase, perhaps to a lesser degree, and this entanglement is responsible for the observed behavior. This hypothesis has been substantiated by undertaking concentration-dependent studies in which it is shown that the reorientation time of the solute increases with an increase in the micellar concentration. In the case of reverse micelles, it has been observed that an enhancement in the water content facilitates solute rotation, which has been rationalized on the basis of solute migration from the hydrated poly(ethylene oxide) region to the poly(ethylene oxide)-water interface within the core.