This report describes an abrasive-free polishing method utilizing nano-bubble water and vacuum high-energy ultraviolet light irradiation as a technique for obtaining ultra-smooth rolled oxygen-free copper. Nano-bubble water was generated by injecting hydrogen and oxygen gas into pure water or electrolyzed water. This nano-bubble water was utilized as the polishing fluid for abrasive-free polishing. Final polishing experiments for removal of nanometer-sized projections under different polishing fluid conditions of pH and oxidation-reduction potential were carried out. The results indicated that the removal rate of projections was increased by vacuum ultraviolet light irradiation, and high pH and high oxidation-reduction potential polishing fluid was suitable for final polishing. In addition, dissolved hydrogen and dissolved oxygen in the polishing fluid were decomposed by vacuum ultraviolet light irradiation, which led to etch-pit generation as surface defects. Therefore, nitrogen nano-bubble water was generated by injecting nitrogen gas into electrolyzed reduced water to decrease the amounts of dissolved hydrogen and dissolved oxygen. High performance final polishing was achieved by utilizing this nitrogen nano-bubble water as the polishing fluid.