The intramolecular electron spin exchange in short nitroxide biradical O=S(OR6)2 (I), where OR6 is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, dissolved in the room temperature ionic liquids (RTILs) 1-octyl-3-methylimidazolium hexafluorophosphate (omimPF6), 1-octyl-3-methylimidazolium tetrafluoroborate (omimBF4), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), and 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF4) has been studied by electron paramagnetic resonance (EPR) spectroscopy as a function of temperature. Temperature variations of the isotropic nitrogen hyperfine splitting constant a were measured from EPR spectra. Thermodynamic parameters of the conformational rearrangements were calculated and compared with literature data. These intramolecular movements in rather rigid short-chain biradical I dissolved in four different RTILs are described well by the Debye–Stokes–Einstein law. Unrestricted density-functional-theory calculations of the geometry and electronic structure of the biradical were carried out using the ORCA program package, and showed that the O=S< group is available for the interaction with anions and cations of RTIL. The possible mechanism of such conformational transitions in biradical I in RTIL is discussed.