High-efficiency rectennas for radio frequency (RF) energy harvesting have been studied for decades, but most of the literature straightforwardly applies the rectenna aiming at dedicated RF sources to this situation, even though the level of input power is significantly different. Since previous studies address antenna design collecting more ambient RF power, the improvement of power conversion efficiency (PCE) has emerged in a scattered way, because the theoretical limit of PCE has not yet been characterized, and the optimal rectenna structure approaching such maximum PCE is still uninvestigated. In this paper, we characterize the performance limit of rectennas with input power ranging from −20 to 0 dBm, proposing optimal rectenna design demonstrating the maximum PCE. The maximum achievable PCE is cast into a mathematical programming problem. Solving this optimization model clarifies the effect of design factors, including operational frequencies, rectifier topologies, and parameterization. To achieve the maximum PCE, our investigation shows that the optimal rectenna structure should not only optimize those design factors but also eliminate the matching circuit between an antenna and a rectifier for ultralow-power scenarios. The resultant PCE at 2.45 GHz is 61.4% and 31.8% at −5 and −15 dBm, respectively, closely approaching the theoretical bound.