Physical-layer Network Coding (PNC) was first proposed for a Two-Way Relay Channel (TWRC) to improve the spectrum efficiency since it allows nodes to transmit simultaneously via a relay node. This technique requires multiple nodes to transmit their packets with accurate synchronization. Therefore, in many works of literature, centralized scheduling with perfect synchronization has been assumed to be employed on top of PNC.Such assumptions are not applicable in general random access multi-hop wireless networks. Therefore, this paper proposes a distributed MAC protocol that supports PNC in static multi-hop wireless networks. The proposed MAC protocol is based on the Carrier Sense Multiple Access (CSMA) strategy, where RTS/CTS frames are used to detect PNC opportunities and to offer the appropriate scheduling of the involved transmissions that should occur simultaneously. This packet exchange process is coordinated by the relay node and was designed to guarantee compatibility with other conventional relaying schemes with specific concerns for the hidden node issues. Our solution was practically tested on a real testbed with different static wireless topologies and several physical settings.With numerical results, we investigate the effectiveness of PNC in distributed wireless multi-hop networks. Compared to the conventional CSMA/CA and the PNC opportunistic (PNCOPP) MAC protocols, the proposed protocol’s performances are advantageous in various scenarios, especially in large networks.