A solid-state (free of internal electrolyte solution) reference electrode based on metallic silver is simply fabricated via a simple electrodeposition from AgNO3. Potentiometry is carried out to study the performance of the solid-state reference electrode in comparison with the commercial Ag/AgCl reference electrode. In addition, the proposed solid-state reference electrode has been integrated with the PPy-modified pH electrode to form an all-solid-state pH sensor, showing the capability of pH measurement. Absence of the internal solution leads to the pH sensor that is convenient to use and maintenance. In addition, the proposed pH sensor is possibly applied to biochemical and medical processes as well as flow infection analysis.