The received radio-frequency (RF) power in farfield RF wireless power transfer (WPT)-with or without simultaneous information transfer-is minuscule due to large propagation loss in wireless media. In such scenarios, adapting to the receiver characteristics by transmit waveform optimization is essential for maximizing the harvested direct current (dc) and, thus, the end-to-end efficiency of an RF WPT system. The receiver efficiency in RF WPT is governed by the RF-to-dc efficiency of the rectifier as well as the impedance mismatch at the antenna and load. In this article, we study the receiver efficiency for any fixed load and, subsequently, present a novel rectifier model that relates the average harvested dc power to the distribution, that is, the histogram, of the instantaneous power levels of the RF signal's envelope over time. The proposed waveform-to-energy harvesting (EH) model enables us to anticipate the average harvested dc power for any waveform, including communication signals as well, given the knowledge of the powerlevel distribution. Consequently, we conduct rigorous waveform optimization to maximize the average harvested dc power and determine the digital baseband signal at the transmitter that does so, namely prove that a pulsed tone at appropriate frequency is optimal for RF WPT. We present a multiband test-bed for determining the receiver efficiency for any digital baseband waveform. The efficacy of the proposed model is corroborated through experiments as well as simulations, which confirm that it is operational as well as accurate in practice and that single-sine pulses yield higher efficiency than basic multisine waveforms, while a pulsed phase shift keying (PSK) is preferable for simultaneous wireless information and power transfer (SWIPT).