The influence of the background concentration of ZnCl2 on the selectivity of Zn(NCS)4(2-)−SE based on QAS to SCN- is studied. The introduction of ZnCl2 into a solution fixes zinc released from the membrane in the form of thiocyanate complex. A high selectivity of the Zn(NCS)4(2-)−SE to SCN- ions is due to the formation of better extractable complexes between zinc and SCN- compared to acidocomplexes of competitive anions. An introduction of 5.0 M ZnCl2 into a solution increases selectivity to SCN- ions by 5 orders of magnitude in the presence of interfering CKO4- ions and more than 4.5 orders of magnitude in the presence of interfering NO3- ions.