Mesoporous low-temperature LiCoO2 nanowire arrays can be directly prepared by a two-step hydrothermal method and they can be easily converted into chain-like high-temperature LiCoO2 nanowire arrays through further calcination. The layered LiCoO2 nanowire arrays exhibit both high gravimetric capacity and areal capacity, while maintaining good cycling stability and rate capability, make them promising for application in microbatteries.