A straightforward protocol for measuring low concentration levels of Ag(I) using bismuth film electrode (BiFE) in combination with anodic stripping voltammetry was developed and studied as a suitable alternative to current methods for detecting the dissolution of silver nanoparticles (Ag NPs). The BiFE was prepared in-situ on the surface of a supporting glassy carbon electrode. Several key operational parameters were examined and optimized, e.g. accumulation potential, accumulation time and concentration of Bi(III). The BiFE revealed good linear operation in the examined concentration range of 10-90 mu g L-1 Ag(I) with r(2) of 0.998, calculated limit of detection (3 sigma) of 2.1 mu g L-1 obtained after 60s accumulation, and favorable repeatability with RSD of 3.6% (50 mu g L-1, n=10). The method was successfully tested through measuring Ag(I) in the supernatant of a commercial Ag NP suspension and the performance was superior to the potentiometric measurement using silver ion-selective electrode. (C) 2015 Elsevier Ltd. All rights reserved.