A solid-state reference electrode (SSRE) is similar to a traditional reference electrode in configuration but has no inner solution. Its layer-by-layer structure influences the stability of an SSRE because of the difference of junction potential between the surfaces. In this work, a SSRE of PVC/PVC-KCl/AgCl/Ag was fabricated and studied. The results confirmed that the proportion of AgCl on the electrode surface affected the stability of reference potential. Besides, PVC membrane coated on the top of electrode controlled the entrance of different ions from the analyte solution. Finally, the optimized SSRE was applied in a electrochemical three-electrode system. In sum, we have built the fabrication process of a PVC-based SSRE and demonstrated its feasibility for sensor applications.