The swelling and exfoliation behaviors of layered potassium ruthenate and the resultant unilamellar crystallites of RuO2.10.2− with nanosheet morphology were studied. The reaction of layered H0.2RuO2.1·0.9H2O with tetrabutylammonium hydroxide (TBA+OH−) was found to be extremely sensitive to the interlayer water content. The use of highly hydrous layered protonic ruthenate was essential for obtaining direct exfoliation. The swelling behavior was also affected by the ratio of TBA+ to ion-exchangeable H+ in the layered compound. At low ratios of TBA+/H+≤1, the layered precursor scarcely exfoliated and mostly deposited as an intercalation compound. In the intermediate TBA+/H+ range, an auburn colloidal suspension containing exfoliated nanosheets was formed, while much larger ratios were less favorable for the exfoliation.