We have demonstrated an interesting approach for the one-pot synthesis of cupric oxide (CuO) nanourchins with sub-100 nm through a sequential dissolution-precipitation process in a water/ethanol system. The first stage produces a precursory crystal [Cu7Cl4(OH)10H2O] that is transformed into monoclinic CuO nanourchins during the following stage. Water is a required reactant for the morphology-controlled growth of different CuO nanostructures. When evaluated for their nonenzymatic glucose-sensing properties, these CuO nanourchins manifest higher sensitivity. Significantly, this water-dependent precursor transformation method may be widely used to effectively control the growth of other metal oxide nanostructures.