A power distribution system capable of network-connecting relay is provided. Power distribution units of the power distribution system execute a master-node-arbitrating process to generate an arbitration result, and respectively switch to a master node mode for being a master node or a slave node mode for being a slave node according to the arbitration result. When being the master node, a power distribution unit receives a monitor command from a remote management device via an external network, and transfers it to the corresponded slave node(s). When being the slave node, a power distribution unit executes the monitor command received from the master node. Therefore, the complexity of building system and the cost of building system can be effectively reduced, and network-connecting relay service can be provided.