Abstract: A suitable system and the best condition were determined for sulfur removal from coal by electrolysis through testing, and the effect of electrolytic conditions on desulfurization rate was studied. At the same time, the influence of electrolysis desulfurization on the structure of coal was inquired into. The results showed that the effect of desulfurization was the best in sodium bromide electrolytic system, the best desulfurization condition was ［NaBr］=1.5 mol/L, I=0.7A, T=343 K, t=4 h and the highest desulfurization rate reached 89%. We found that with increasing electrolytic conditions, desulfurization rate increased at first, and then kept constant. The analysis of IR spectrum showed that the structure of coal wasn't destroyed.