<正> Three empirical rules of interfacial potential and Gibb's energy with the radius,chargenumber of transfer ions and dielectric constant of organic phase are obtained for the ion transfer acrossthe liquid-liquid interface,which are verified by the transfer of simple anions,dye ions and metalions facilitated by neutral ionophores across the interface between water and some organic solvents,and deduced theoretically based on the electrostatic interaction of ion and high-permittivity solvent.The rules are proved to be effective of choosing supporting electrolytes and searching for new transfersystem which follows the rule that r/n of transfer ion should be larger than that of electrolytes ion inwater phase and less than that in organic phase.A rule for judgement of the charge sign of transferion is suggested firstly based on the relationship between interfacial half-wave potential and dielectricconstant of organic phase.