Feasibility of high-sulfur bauxite electrolysis desulfurization was examined using the electrochemical characterization, XRD, DTA, and FTIR. The cyclic voltammetry curves indicated that bauxite water slurry (BWS) electrolysis in NaOH system was controlled by diffusion. Additionally, the desulfurization effect of NaCl as the electrolyte was significantly better than that of NaOH as an electrolyte. As the stirring rate increased, the desulfurization ratio in NaCl system was not increased obviously, while the desulfurization ratio in NaOH system increased significantly, indicating further that electrolysis desulfurization in NaOH solution was controlled by diffusion. According to XRD, DTA, and FTIR analysis, the characteristic peaks of sulfur-containing phase in bauxite after electrolysis weakened or disappeared, indicating that the pyrite in bauxite was removed from electrolysis. Finally, the electrolytic desulfurization technology of bauxite was proposed based on the characteristics of BWS electrolysis.