A valve stem structure disposed at a rim of a tire of a vehicle for connecting to an electronic tire pressure monitoring device in the tire is provided. The valve stem structure includes a tube, an air core, and a conducting wire. The tube has a first inlet, a first outlet communicating with an inner space of the tire, and a second outlet. The air core is switchably disposed at the first inlet, and a compressed air is injected into the tire via the first inlet and the first outlet by switching the air core. The conducting wire is disposed in the tube, and an end of the conducting wire extends out of the tube via the second outlet to be electrically connected to the electronic tire pressure monitoring device. A power source charges the electronic tire pressure monitoring device via the conducting wire.