Elucidating the role of sulfur on the structure of silicate glasses and melts at elevated pressures and temperatures is important for understanding transport properties, such as electrical conductivity and viscosity, of magma oceans and mantle-derived melts. These properties are fundamental to modeling the evolution of terrestrial planets and moons. Despite several investigations of sulfur speciation in glasses, questions remain regarding the effect of S on complex glasses at highly reducing conditions relevant to Mercury. Glasses were synthetized with compositions representative of the Northern Volcanic Plains of Mercury and containing quantities of S as high as 5 wt.%. Multiple spectroscopic methods and microprobe analyses were employed to probe the glasses, including in situ impedance spectroscopy at 2- and 4-GPa pressures and temperatures up to 1740 K using a multi-anvil press, 29Si NMR spectroscopy, and Raman spectroscopy. Electrical activation energies (Ea) in the glassy state range from 0.56 to 1.10 eV, in agreement with sodium as the main charge carrier. The electrical measurements suggest that sulfide improves Na+ transport and may overcome a known impeding effect of the divalent cation Ca2+. The glass transition temperature lies between 700-750 K, and for temperatures up to 970 K Ea decreases (0.35-0.68 eV) and the conductivities of the samples converge (~5-8 *10-3 S/m). At Tquench, the melt fraction is 50-70% and melt conductivity varies from 0.7 to 2.2 S/m, with the sample containing 5 wt.% S the most conductive among the set. 29Si NMR spectra reveal that a high fraction of S bonds with Si in these complex glasses, an important insight that has not been recognized previously. Raman spectra and maps reveal regions rich in Ca-S or Mg-S bonds. The evidence of sulfide interactions with both Si and Ca/Mg suggest that alkaline earth sulfides can be considered weak network modifiers in these glasses, under highly reduced conditions. Experimental data from impedance spectroscopy, NMR spectroscopy, Raman spectroscopy and electron microprobe analyses. The description of the experiments and analyses is explained the manuscript. # Title of Dataset Data used in manuscript GCA-D-23-00571 entitled Experimental Investigation of the Bonding of Sulfur in Highly Reduced Silicate Glasses and Melts by A. Pommier, M. J. Tauber, H. Pirotte, G.D. Cody, A. Steele, E.S. Bullock, B. Charlier, and B.O. Mysen (Geochimica et Cosmochimica Acta). The spreadsheet lists all the measurements shown in the figures of the manuscript. Each tab correspond to a figure: -Figures 2 and 3: electron microprobe analyses. -Figures 4 and 5: impedance spectroscopy -Figure 6: NMR spectroscopy -Figures 8 and 9: Raman spectroscopy -Figure 10: NBO/T estimates The reader is referred to the manuscript for details about the experimental procedures and results. ## Description of the data and file structure * Figure 2 tab: Each sample name starts with BBC. For each sample, electron microprobe analyses are shown for traverses across the sample and the content of each oxide is in wt.%. * Figure 3 tab: Microprobe traverse in sample BBC16. The content of each oxide is in wt.%. * Figure 4: Impedance spectra of samples BBC13 and BBC17 at selected temperatures. For each temperature, the different columns correspond to the frequency, time, real component (Z') and imaginary component (Z"). * Figure 5 tab: electrical resistance (R) and conductivity (EC) of different samples as a function of temperature (T). Each sample name starts with BBC. For each sample, the different columns correspond to temperature (in degC and K), inverse T, resistance, conductivity and Ln (conductivity). * Figure 6: NMR spectra for four starting glasses (VT48, 52, 53, 54). The first column is the chemical shift, and the other columns correspond to the intensity of each sample. * Figure 7: Raman spectrum of starting glass VT55. The first column is the Raman shift, and the second column corresponds to the intensity of the sample. * Figure 8: Raman spectra of sulfide components in starting glass VT52 and samples from experiments BBC17 and BBC18. For each sample, the first column is the Raman shift, and the second column corresponds to the intensity of the sample. Copyright: CC0 1.0 Universal (CC0 1.0) Public Domain Dedication