Natural convection actuated by electrochemically-generated density gradients at microelectrodes was investigated under different conditions by simultaneously visualizing fluid flow with the electrochemical response. The studies elucidate deviations of electrochemical behavior from theoretical expectations and parameters that control natural convection, which can be exploited in electroanalysis, microfluidics, and electrodeposition. Experiments involved an enclosed, small volume containing 0.00475-0.095 M each of K 3 Fe(CN) 6 and K 4 Fe(CN) 6 in 0.095 M KCl, over concentric gold disk (radius: 16-156 μm) and ring (inner radius: 200-1600 μm, outer radius: 250-2000 μm) microelectrodes. Fluid velocities were obtained with video microscopy by tracking 10-μm beads added to the solution. Flow radiates near the disk either inwardly or outwardly at the bottom of the cell and reverses direction at the top, producing a vertical circulation. Maximum velocities of ∼10 μm/s were measured for the 156-μm disk in 0.095 M. After application of potential or current, the onset of natural convection occurred at shorter times (6 s) than measurable affects in electrochemical current/voltage responses (tens of seconds). Convection from density gradients occurred without corresponding changes in electrochemical responses for the 78-μm disk at the lowest concentration (0. We quantify with fluid velocity measurements the natural convection that is induced by electrochemically-generated density gradients at microelectrodes in a small volume system initially containing a static solution of redox species and where the Reynolds number is less than unity (see the Supplementary Material). Electrochemical reactions at the electrode-solution interface and the associated counter ion movement in the electrode vicinity lead to a density mismatch with respect to the bulk solution, thus generating "natural" convection of the fluid due to the relative changes in buoyant forces. Here, the effects of natural convection were measured experimentally by the changes in electrode current, potential, and localized fluid velocity, the latter of which is especially unique to this work for the small dimensions, currents, and concentrations employed here. Understanding natural convection from electrochemical processes in small, confined volumes is important for implementing new mixing strategies in microfluidic systems, harnessing better control over the morphology of electrodeposited films, and properly interpreting electrochemical signals from microelectrochemical analysis in comparison to theoretical expectations.When the conversion between a reactant and product at an electrode involves a change in the charge, the movement of ions to achieve neutrality can create a localized change in density. Volume elements that become less dense will rise, and those that become more dense will sink, hence leading to mass transfer by natural convection, which further affects the concentration distribution near the electrode-solution interface, and thus may cause the electrode...