Size effect and photocatalytic activity of CuO sheet-like nanostructures, which were synthesized by a facile solution phase chemical method with ethanol and water mixture as solvent, have been investigated by UV–vis absorption spectrum and photocatalytic degradation of pollutant rhodamine B (RhB). UV–vis absorption spectrum indicated that the band gap energy was about 2.31eV for the as-prepared CuO nanostructures. The result indicates that the band gap energy of the CuO sheet-like nanostructures is much larger than value of bulk CuO crystals, showing that the CuO sheet-like nanostructures exhibit a strong quantum size confinement effect. The photocatalytic activity indicates that the as-synthesized CuO sheet-like nanostructures show an enhanced photocatalytic activity with 96.7% degradation of RhB after 9h reaction under UV light irradiation, which was much higher than that of commercial CuO powders (39.6%).