Strongly encouraged and supported by Stanislav S. Dukhin the authors of this article recently designed, built and tested a new device for the simultaneous determination of zeta potential and surface conductivity from streaming potential and streaming current measurements across rectangular slit channels formed between two planar samples. In this Microslit Electrokinetic Set-up (MES) the planar samples are adjusted in parallel to form a channel of variable height which can become as narrow as about 1 μm. Due to this key feature of the device electrokinetic measurements can be performed at conditions where surface conductivity can be neglected and at conditions where surface conductivity provides a substantial part of the total channel conductivity. Utilizing the novel set-up, zeta potential and surface conductivity data can be obtained for a wide variety of materials which can be prepared as thin films on top of planar, macroscopic glass carriers. In order to demonstrate the potentialities of the advanced experimental technique of electrokinetic surface characterization we discuss three examples reflecting different levels of complexity of the analysed solid/liquid interface: (1) The charge formation at unpolar polymers without dissociating surface functions is studied referring to an inert, plasma-deposited fluoropolymer layer (PDFP) in simple electrolyte solutions. An extended evaluation of the experimental data of zeta potential and surface conductivity is given; (2) Further, grafted polypetide chains bearing dissociating side groups (polyglutamic acid and polylysine) were characterized with regard to the pH-depended variation of zeta potential and surface conductivity to provide new insights into the interrelation of charge density and conformation; (3) Finally, adsorbed fibrinogen on top of plasma-deposited fluoropolymer was studied by zeta potential and surface conductivity measurements as an example for highly hydrated macromolecular adsorption layers.