The effect of photo-stimulated adsorption of cationic (polyethylenimine, PEI) and anionic (glucose oxidase, GOx) polyelectrolyte molecules on C-V characteristics of a electrolyte/insulator/semiconductor structure was investigated. We obtained that illumination of semiconductor during the adsorption of PEI increases a shift of the flat band potential by 29% and 45% for n-Si and p-Si, respectively. Furthermore, depending on a Si conductivity type, the photo-stimulated adsorption of GOx molecules either increases (for n-Si/PEI) or decreases (for p-Si/PEI) the C-V shift, which was explained by corresponding changes of enzyme molecules on the surface, respectively. Our research is useful in fabrication of potentiometric biosensors since the growth of enzyme molecules density on the surface of the semiconductor transducer increases the threshold sensitivity of the sensor.