2,2,6,6-Tetramethylpiperidine-1-yloxyl derivatives substituted with either hydrogen bonding [-OH, -OSO(3)H] or ionic [-OSO(3) (-)Na(+), -OSO(3) (-)K(+), N(+)(CH(3))(3)I(-), N(+)(CH(3))(3) N(-)(SO(2)-CF(3))(2)] substituents are investigated in 1-butyl-3-methylimidazolium tetrafluoroborate over a wide temperature range covering both glassy and viscous states. The Vogel-Fulcher-Tammann equation describes the temperature dependence of the ionic liquid viscosity. Quantum chemical calculations of the spin probes at the UB3LYP/6-311(2d,p++) level are done to describe the dependence of the spin density on nitrogen on the substitution pattern of the 4-position of the probe. The results of these calculations are also used to understand the experimental results obtained by applying the Spernol-Gierer-Wirtz theory to analyze the viscosity dependence of the rotational correlation time of the spin probes. Significant differences are found between 2,2,6,6-tetramethylpiperidine-1-yloxyl and its derivatives containing substituents that are able to form hydrogen bonds with the ionic liquid. Moreover, derivatives substituted with ionic groups at the 4-position have a large effect on temperature-induced solvent viscosity, as this is particularly dependent on the nature of the substituent at the 4-position. These dependencies include the temperature region that can be used to describe interactions between the spin probes and the ionic liquid, diffusion into the free volume during non-activated (neutral spin probes) and activated (charged spin probes) processes. Additional parameters are the radii of the ionic liquid and the spin probes, which are calculated and measured approximately. In addition, the temperature dependence of the isotropic hyperfine coupling constants of the spin probes results in information about the micropolarity of the ionic liquid. At room temperature, this is comparable to that of the solvent dimethylsulfoxide.