Abstract: Porous ionic liquids have demonstrated excellent performance in the field of separation, attributed to their high specific surface area and efficient mass transfer. Herein, task-specific protic porous ionic liquids (PPILs) were prepared by employing a novel one-step coupling neutralization reaction strategy for extractive desulfurization. The single-extraction efficiency of PPILs reached 75.0% for dibenzothiophene. Moreover, adding aromatic hydrocarbon interferents resulted in a slight decrease in the extraction efficiency of PPILs (from 45.2% to 37.3%, 37.9%, and 33.5%), indicating the excellent extraction selectivity of PPILs. The experimental measurements and density functional theory calculations reveal that the surface channels of porous structures can selectively capture dibenzothiophene by the stronger electrophilicity (Eint (HS surface channel/DBT) = −39.8 kcal mol−1), and the multiple extraction sites of ion pairs can effectively enrich and transport dibenzothiophene from the oil phase into PPILs through π···π, C–H···π and hydrogen bonds interactions. Furthermore, this straightforward synthetic strategy can be employed in preparing porous liquids, offering new possibilities for synthesizing PPILs with tailored functionalities.