We show that when particles are suspended in an electrolyte confined between corrugated charged surfaces, electrokinetic flows lead to a new set of phenomena such as particle separation, mixing for low-Reynolds micro-and nano-metric devices and negative mobility. Our analysis shows that such phenomena arise, for incompressible fluids, due to the interplay between the electrostatic double layer and the corrugated geometrical confinement and that they are magnified when the width of the channel is comparable to the Debye length. Our characterization allows us to understand the physical origin of such phenomena therefore shading light on their possible relevance in a wide variety of situations, ranging from nano-and micro-fluidic devices to biological systems.PACS numbers: 82.39. Wj,47.56.+r,47.61.Fg The recent development of nano-and micro-fluidic devices [1] as well as cellular regulation mechanisms and cellular signaling [2] rely on the transport of ions across channels or pores whose sections range from the nanometric to the micrometric scale [3][4][5]. The transport across such conduits has been characterized, even for varying-section channels [6][7][8][9][10][11], assuming that the channel width, h(x), is large compared to the Debye length, κ −1 , over which the electrolyte charge distributes in the neighborhood of the charged channel wall (κh(x) ≫ 1), or in the absence of electrolytes [12]. Nowadays, the continuous process of device miniaturization and the widening of the range of achievable salt concentrations require an understanding of the behavior of such systems when the relevant length scales compete with each other [13]. Such regimes are already exploitable in different microand nano-fluidic experiments [3,4] and can be relevant in a variety of biological systems [14,15].In this Letter we will show that, precisely in this regime, i.e. when the Debye length and the channel aperture are comparable in size, κh(x) ∼ 1, an electrolyte embedded in a corrugated channel develops new transport regimes that can be exploited to separate suspended particles, control electric and mass currents and eventually induce negative mobility. When κh(x) ∼ 1, the electrolyte response to external forcing, such as electrostatic fields, is very sensitive to the channel shape and it develops a recirculating region in which the electrolyte flows on the opposite direction as compared to the average volume flow, as shown in Fig. 1.A. Such a phenomenon, typical for incompressible fluids, is due to the interplay between the electrostatic double layer and the varying geometrical confinement and its magnitude is significantly amplified when κh(x) ∼ 1. We coin this regime entropic electrokinetics since the phenomena we identify can only arise due to the spatially varying constriction induced by the geometrical confinement. This variation affects the local spatial distribution of ions, essentially controlled by the interplay between the wall charge and the ion entropy. We will show that the entropic variations in the charge density i...