In this research, a technique incorporating dual-asymmetry electrokinetic flow (DAEKF) was applied to a nanoCE electrochemical device for the pre-concentration and detection of catecholamines. The DAEKF was constructed by first generating a zeta-potential difference between the top and bottom walls, which had been pre-treated with O-2 and H2O surface plasma, respectively, yielding a 2-D gradient shear flow across the channel depth. The shear flow was then exposed to a varying zeta-potential along the downstream direction by control of the field-effect in order to cause downward rotational flow in the channel. By this mechanism, almost all of the samples were effectively brought down to the electrode surface for analysis. Simulations were carried out to reveal the mechanism of concentration caused by the DAEKF, and the results reasonably describe our experiment findings. This DAEKF technique was applied to a glass/glass CE electrochemical nanochip for the analysis of catecholamines. The optimum detection limit was determined to be 1.25 and 3.3 nM of dopamine and catechol, respectively. A detection limit at the zeptomole level for dopamine can be obtained in this device, which is close to the level released by a single neuron cell in vitro.