New sorbents for the desulfurization of liquid fuels were developed using pi-complexation. Vapor-phase adsorption isotherms were investigated to understand the interaction between benzene/thiophene and various kinds of sorbents, including Ag-Y, Cu-Y, Na-Y, H-USY, Na-ZSM-5, activated carbon, and modified activated alumina. Compared to Na-Y, Cu-Y and Ag-Y adsorbed significantly larger amounts of, both thiophene and benzene at low pressures, as a result of pi-complexation with Cu+ and Ag+. Molecular orbital calculations confirmed that the relative strengths of pi-complexation lie in the order thiophene > benzene and Cu+ > Ag+. The experimental heats of adsorption for pi-complexation are in excellent agreement with theoretical molecular orbital predictions. Na-ZSM-5 and activated carbon could also adsorb small amounts of thiophene and benzene at low pressures. The sorbent capacities for thiophene at the low pressure of 2.3 x 10(-5) atm were 0.92 molecule/Cu+ and 0.42 molecule/Ag+ and followed the order Cu-Y and Ag-Y much greater than Na-ZSM-5 > activated carbon > Na-Y > modified alumina and H-USY. The separation factors of thiophene over benzene (at low concentrations of thiophene) calculated from pure component adsorption isotherms exhibited the trend Ag-Y > Na-ZSM-5 > Cu-Y approximate to activated carbon much greater than Na-Y much greater than H-USY approximate to modified activated alumina.