The shape and the surface charge of microchannels are critical parameters for ionic and mass transport in microfluidic systems. A great number of studies and developments have been carried out in order to optimize these features separately. We propose to consider them together within a new fundamental parameter for microfluidics, that we named the Volumic Surface Charge (VSC), which is the ratio of the surface charge to the section height in planar microchannels. The non-linear effects induced by rapid VSC variations can result in selective preconcentration processes, which can be used for a simultaneous preconcentration and separation of biomolecules within simple straight channels. In this review, we first present 3 different techniques that we developed to tune the VSC either by surface chemical patterning, integration of polarisable interfaces or geometrical constrictions. The proof of concept of the selective preconcentration using VSC variations will be presented on the basis of experimental results obtained with fluorescent probes and numerical simulations.