We proposed and developed an exfoliation process for layer-structured NaxCoO2 to prepare CoO nanosheets. Na+ ion exchange by acid treatment was utilized to expand the spacing between the two CoO2 layers in NaxCoO2. Ethylamine was then effectively utilized for the exfoliation of cobalt oxide sheets having nanometer-order thickness and high aspect ratio. CoO nanosheets were observed by TEM micrographs and electron diffraction patterns after drying. Further efforts are needed for the application of exfoliated sheets to an integration process to fabricate self-assembled nanomaterials such as desired layer structures composed of two (or more) kinds of nanosheets.