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The flower-like Cu2O nanostructures were hydrothermally synthesized without using any template or surfactant. The influences of hydrothermal temperature, reaction time and reactants concentrations on the growth of nanostructures were investigated in detail. The samples were characterized by scanning electron microscope (SEM) and X-ray powder diffraction (XRD). Cu2O crystals with different shapes, i.e., flower-like (F-product) cubic box (CB-product) and cubic box with holes in each face (CBH-product), were synthesized by controlling the synthesis parameters and explored for CO catalytic oxidation. It was found that F-product showed higher catalytic than others. [ABSTRACT FROM AUTHOR]