An approach is proposed aimed at sensing single-ion activities with ionophore-based bulk optodes. The approach relies on the stabilization of the Galvani potential difference at the optode/sample interface, e.g. by use of tetrabutylammonium tetrabutylborate (Q+B−): a moderately lipophilic electrolyte used in solid reference electrodes. The pH/Na optode is successfully utilized as a model system. Optodes modified with Q+B− show practically the same response to pH at distinctively different concentrations of sodium in samples.