Photoluminescence (PL) from Si and SiGe is comprehensively modified by Au NPs under excitation without surface plasmon resonance. Moreover, the PL sensitively depends on the size of the Au NPs, the excitation power and the thickness of the Si layer between the Au NPs and SiGe. A model is proposed in terms of the electrostatic effects of Au NPs naturally charged by electron transfer through the nanoscale metal/semiconductor Schottky junction without an external bias or external injection of carriers. The model accounts well for all the unique PL features. It also reveals that Au NPs can substantially modify the energy band structures, distribution and transition of carriers in the nanoscale region below the Au NPs. Our results demonstrate that Au NPs on semiconductors can efficiently modulate light-matter interaction.