We report about the modulation of the electrical properties of thin film solar cells due to the incorporation of size-selected Au nanostructures (NSs) at a textured FTO/p–i–n interface. By increasing the Au NSs size, the analyses of current-voltage characteristics show lower Schottky barrier heights and the gradual reduction of the open-circuit voltages (VOC). The optical measurements show higher parasitic absorption by larger Au NSs that reduces the amount of radiation transmitted by the transparent to absorber layer. This process decreases the number of photo-generated carriers and may explain the VOC reduction related to the devices with larger Au NSs at the interface. So, the correlation between materials properties and device performances was established.