Ash in Guiding subbituminous coal (GSBC) was removed by treatment with dilute acids. The treated GSBC (TGSBC) was extracted with isopropanol (IP) to afford IP-extractable fraction (IPEF). TGSBC was sequentially extracted with petroleum ether, carbon disulfide, acetone, and methanol. Octane-1-thiol and thiophene were selected as model compounds (MCs) for organic sulfurs in GSBC. MCs and extracted residue (ER) of TGSBC were electrolyzed in an aqueous NaCl solution. Reaction mixtures from the electrolysis of MCs were extracted with cyclohexane. The electrolyzed extracted residue (EER) was extracted with the same method as TGSBC. The extracts were analyzed with gas chromatography/mass spectrometry (GC/MS). ER and EER were analyzed with Fourier transform infrared (FTIR) spectrometry. Three organic sulfurs were detected in IPEF from TGSBC with GC/MS. FTIR analysis shows that ER electrolysis increased oxygen-containing functional groups but decreased organic sulfurs. Disulfide, sulfoxide, sulfone, and sulfonic acid were detected by GC/MS and FTIR analyses. The mechanism for removal of organic sulfur during GSBC electrolysis was discussed.