A network system with wake-up on LAN (WOL) mechanism and a wake-up on LAN method are disclosed. The network system includes: a first network device in a first local area network; a second network device in a second local area network, wherein the first local area network and the second local area network are different; and, a match server in a wide area network, wherein the first network device and the second network device perform data transmission through the match server.