Abstract: | Microfluidic devices were designed to electrochemically detect in a two‐phase flow the velocity, size and content of aqueous droplets containing redox species. The principle of these determinations is based on the analysis of a unique chronoamperometric response recorded during the passage of a droplet over channel microelectrodes. Two configurations of electrochemical cell with different geometries were investigated both theoretically and experimentally. Velocity and size of droplets, as well as internal recirculating convection within droplets, were evaluated from chronoamperometric curves by specific transition times depending on the cell configuration. In addition, the droplet content was probed from the Faradaic current controlled by mass transport and by internal hydrodynamic regime. For droplet velocity and size, experimental data were systematically compared to optical measurements. All the results demonstrated the high performance of the electrochemical detection reached under these conditions. They successfully validate the concept of self‐consistent electrochemical detections of aqueous droplets within microchannels for the simultaneous determination of their velocity, size and content. |