As polyelectrolytes play a more and more important role in electrochemical fields, further understanding of the electrode-polyelectrolyte interface is in high demand. Surface-enhanced Raman spectroscopy (SERS) is utilized widely in electrode-solution interface research due to its ultra-high sensitivity, but is still rarely in the study of the electrode-polyelectrolyte interface due to difficulties in constructing appropriate electrochemical in situ devices. Additionally, the reported electrochemical in situ Raman works on the electrode-polyelectrolyte interface have a common problem of the coexistence of electrode-solution interfaces and electrode-polyelectrolyte interfaces. Here, we used screen printing electrodes (SPE) with a compact planar three-electrode structure to carry out a new electrochemical in situ SERS test method, which was suitable for the study of the electrode-polyelectrolyte interface. Polyelectrolyte membranes can be conveniently and closely coated on the SPE's planar three electrodes to achieve isolated electrode-polyelectrolyte interfaces without electrode-solution interfaces coexisting. Strongly potential-dependent signals were obtained from the Pt-Nafion™ interface directly across the Nafion™ membrane, which verifies that this method is practical for the electrochemical in situ SERS study of the electrode-polyelectrolyte interface.