A photovoltaic (PV)-assisted CMOS rectifier was developed for efficient energy harvesting from ambient radio waves as one example of the synergistic energy harvesting concept. The rectifier operates truly synergistically. A pn junction diode acting as a PV cell converts light energy to DC bias voltage, which compensates the threshold voltage (Vth) of the MOSFETs and enhances the radio frequency (RF) to DC power conversion efficiency (PCE) of the rectifier even under extremely low input power conditions. The indoor illuminance level was sufficient to generate gate bias voltages to compensate Vths. Although the same PV cell structure for biasing nMOS and pMOS transistors was used, photo-generated bias voltages were found to become unbalanced due to the two-layered pn junction structures and parasitic bipolar transistor action. Under typical indoor lighting conditions, a fabricated PV-assisted rectifier achieved a PCE greater than 20% at an RF input power of -20dBm, a frequency of 920MHz, and an output load of 47kΩ. This PCE value is twice the value obtained by a conventional rectifier without PV assistance. In addition, it was experimentally revealed that if symmetric biasing voltages for nMOS and pMOS transistors were available, the PCE would increase even further.