The pyridinium-based ionic liquids (ILs) N-butylpyridinium tetrafluoroborate ([BPy][BF4]), N-hexylpyridinium tetrafluoroborate ([HPy][BF4]), and N-octylpyridinium tetrafluoroborate ([OPy,][BF4]) were found to be effective for the selective removal of aromatic heterocyclic sulfur compounds from diesel at room temperature. The results suggested that the structure and size of the cation greatly affect the extractive performance of ILs. The extractive performance using pyridinium-based ILs followed the order [BPy][BF4] < [HPy][BF4] < [OPy][BF4], and for the IL, the sulfur removal selectivity of sulfur compounds followed the order thiophene (TS) < benzothiophene (BT) < dibenzothiophene (DBT) under the same conditions. The pyridinium-based ILs would not contaminate the diesel due to their insolubility. On the other hand, diesel has a certain solubility in pyridinium-based ILs, varying from 0.49 wt % for [BPy][BF4] to 1.97 wt % for [OPy][BF4]. According to the results, [HPy][BF4] and [OPy][BF4] might be used as promising solvents for the extractive desulfurization of diesel.