In this paper, we propose a framework for cross-layer analysis of multi-static passive RFID systems. The model takes into account details of the shared wireless channel, including fading and capture effect, whereas, at the medium access control (MAC) layer, the anti-collision mechanism proposed in the EPC Generation 2 standard is taken as a reference. To address the complexity of the system model, we rely on a semi-analytical approach, that combines a moment matching approximation method to abstract the physical layer and Monte-Carlo simulations to describe the MAC dynamics. Furthermore, based on the space diversity feature offered by the multi-static settings, we introduce the concept of capture diversity and propose a modification to the standard to fully support this form of diversity. Numerical results show the impact of deployment conditions and the relative positions of interrogator, tags, and detection points on the performance of tags’ identification. We show how the number of detection points impacts the system performance under various channel conditions and MAC parameters’ settings. Finally, we validate the proposed update of the MAC protocol, showing substantial performance improvement with respect to the standard collision resolution policy.