The interface between two immiscible electrolyte solutions (ITIES) has become a very powerful analytical platform for sensing a diverse range of chemicals (e.g., metal ions and neurotransmitters) with the advantage of being able to detect nonredox electroactive species. The ITIES is formed between organic and aqueous phases. Organic solvent identity is crucial to the detection characteristics of the ITIES [half-wave transfer potential (E 1/2 ), potential window range, limit of detection, transfer coefficient (α), standard heterogeneous ion-transfer rate constant (k 0 ), etc.]. Here, we demonstrated, for the first time at the nanoscale, the detection characteristics of the NPOE/water ITIES. Linear detection of the diffusion-limited current at different concentrations of acetylcholine (ACh) was demonstrated with cyclic voltammetry (CV) and i−t amperometry. The E 1/2 of ACh transfer at the NPOE/water nanoITIES was −0.342 ± 0.009 V versus the E 1/2 of tetrabutylammonium (TBA + ). The limit of detection of ACh at the NPOE/water nanoITIES was 37.1 ± 1.5 μM for an electrode with a radius of ∼127 nm. We also determined the ion-transfer kinetics parameters, α and k 0 , of TBA + at the NPOE/water nanoITIES by fitting theoretical cyclic voltammograms to experimental voltammograms. This work lays the basis for future cellular studies using ACh detection at the nanoscale and for studies to detect other analytes. The NPOE/water ITIES offers a potential window distinct from that of the 1,2-dichloroethane (DCE)/water ITIES. This unique potential window would offer the ability to detect analytes that are not easily detected at the DCE/water ITIES.

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