Rectennas, which mainly consist of an antenna, matching network, and rectifier, are used to harvest radiofrequency energy in order to power tiny sensor nodes, e.g., the nodes of the Internet of Things. This paper demonstrates for the first time, the existence of an optimum voltage gain for high-pass L-matching networks used in rectennas by deriving an analytical expression. The optimum gain is that which leads to maximum power efficiency of the rectenna. Here, apart from the L-matching network, a Schottky single-diode rectifier was used for the rectenna, which was optimized at 868 MHz for a power range from -30 dBm to -10 dBm. As the theoretical expression depends on parameters not very well-known a priori, an accurate search of the optimum gain for each power level was performed via simulations. Experimental results show remarkable power efficiencies ranging from 16% at -30 dBm to 55% at -10 dBm, which are for almost all the tested power levels the highest published in the literature for similar designs.