ABSTRACT: Malachite (Cu₂(OH)₂CO₃) with a hierarchical sphere-like architecture has been successfully synthesized via a simple and mild hydrothermal route in the absence of any external inorganic additives or organic structure-directing templates. Powder X-ray diffraction, scanning electron microscopy, and Fourier transmission infrared spectrometry are used to characterize various properties of the obtained malachite samples. The hierarchical malachite particles are uniform spheres with a diameter of 10-20 mm, which are comprised of numerous two-dimensional micro-platelets paralleling to the sphere surface. The initial concentration of reagents, the hydrothermal reaction time and temperature are important factors, which dominantly affect the evolution of crystal morphologies. The growth of the hierarchical architecture is believed to be a layer-by-layer growth process. Further, copper oxide with the similar morphology can be easily obtained from the as-prepared malachite.