Lamellar structured ultrathin manganese oxide nanoplates have been synthesized from thermal decomposition of manganese(II) acetylacetonate in the presence of 2,3-dihydroxynaphthalene, which promoted two-dimensional (2-D) growth by acting not only as a strongly binding surfactant but also as a structure-directing agent. Ultrathin manganese oxide nanoplates with a thickness of about 1 nm were assembled into a lamellar structure, and the width of the nanoplates could be controlled from 8 to 70 nm by using various coordinating solvents. X-ray absorption near-edge structure (XANES) spectra at the Mn K edge clearly showed that the nanoplates are mainly composed of Mn(II) species with octahedral symmetry. These hydrophobic manganese oxide nanoplates were ligand-exchanged with amine-terminated poly(ethyleneglycol) to generate water-dispersible nanoplates and applied to T1 contrast agents for magnetic resonance imaging (MRI). They exhibited a very high longitudinal relaxivity (r₁) value of up to 5.5 mM^–1s^–1 derived from their high concentration of manganese ions exposed on the surface, and strong contrast enhancement of in vitro and in vivo MR images was observed with a very low dose.