This work discusses nuclear magnetic relaxation effects in glycerol subject to a strong electric field. The methods used are 1.5 T magnetic resonance imaging (MRI), referenced by 9.4 T nuclear magnetic resonance (NMR). While MRI allows a glycerol probe to be sampled with a high voltage (HV) of 16 kV applied to the probe, NMR provides precise molecular data from the sample, but the sample cannot be tested under HV. Using MRI, the recording of magnetic relaxation times was possible while HV was applied to the glycerol. NMR spectroscopy was used to confirm that MRI provides a reasonably accurate estimation of temperature. The applied HV was observed to have a negligible effect on the spin–lattice relaxation time T1, which represents the energy release to the thermal bath or system enthalpy. In contrast to that, the spin–spin relaxation time T2, which does represent the local entropy of the system, shows a lower response to temperature while the liquid is electrically stressed. These observations point toward a proton population in electrically stressed glycerol that is more mobile than that found in the bulk, an observation that is in agreement with previously published results for water.