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The past years have witnessed increasing research interest in achieving passive human localization with commodity WiFi devices. However, due to the fundamental limited spatial resolution of WiFi signals, it is still very difficult to achieve accurate localization with existing commodity WiFi devices. To tackle this problem, in this paper, we propose to exploit the degree of freedom provided by the Intelligent Reflecting Surface (IRS), which is composed of a large number of controllable reflective elements, to modulate the spatial distribution of WiFi signals and thus break down the spatial resolution limitation of WiFi signals to achieve accurate localization. Specifically, in the single-person scenario, we derive the closed-form solution to optimally control the phase shift of the IRS elements. In the multi-person scenario, we propose a Side-lobe Cancellation Algorithm to eliminate the near-far effect to achieve accurate localization of multiple persons in an iterative manner. Extensive simulation results demonstrate that without any change to the existing WiFi infrastructure, the proposed framework can locate multiple moving persons passively with sub-centimeter accuracy under multipath interference and random noise.