An unusual intercalation of lithium zinc oxide (LiZnO) is produced by the electrochemical lithium insertion into a ZnO film electrode. As its isolated unit. LiOZn and LiOZn+ molecules exhibit a new type of hypervalent species with two heterometal atoms and one oxygen atom. Time-of-flight mass spectrometry has also been employed to give direct experimental evidence for the existence of LiOZn+ generated by laser ablation of a composite Li/ZnO target in a high vacuum. The stability and structure of the hypervalent molecule LiOZn and its ion as well as its isomer are investigated by ab initio molecular orbital calculations. The overlap between the 2s orbital in Li, the 2p, orbital in O, and the 4s orbital in Zn should be responsible for a linear structure of these molecules. The extra one electron beyond the usual octet in LiOZn may play an important role in the binding between a lithium atom and a zinc atom around the central oxygen atom.