The specific interaction of N-tetradecylisoquinolinium (C(14)Iq(+)) with Cl- and Br- has been detected in the voltammetry of ion transfer and electrocapillarity at the interface between an aqueous solution (W) and a room-temperature ionic liquid (RTIL), N-tetradecylisoquinolinium bis(pentafluoroethylsulfonyl) imide ([C(14)Iq(+)][C2C2N-]). This specific interaction also makes the transfer of Cl- and Br- into [C(14)Iq(+)][C2C2N-] energetically more favorable in comparison with that of F- and SO42-. The width of the polarized potential window in ion-transfer voltammetry at the [C(14)Iq(+)][C2C2N-]\W interface is significantly narrower because of the transfer of anions from W to RTIL. The degree of affinity of the anion with C(14)Iq(+) agrees with the Hofmeister series. Such an ion-pair formation of anions in W with cations in the RTIL is much weaker when the cation constituting the RTIL is a symmetric tetraheptylammonium ion.