In this paper, mesoporous CuO with a novel architecture was synthesized through a conventional hydrothermal approach followed by a facile sintering procedure. HR-TEM analysis found that mesoporous CuO with an interconnected pore structure has exposed high-energy crystal planes of (002) and (200). Theoretical calculations indicated that the high-energy crystal planes have superior adsorption capacity for H+ ions, which is critical for the excellent adsorption and remarkable photocatalytic activity of the anionic dye. The adsorption capacity of CuO to methyl orange (MO) at 0.4 g/L was approximately 30% under adsorption equilibrium conditions. We propose a state-changing mechanism to analyze the synergy and mutual restraint relation among the catalyst CuO, H+ ions, dye and H2O2. According to this mechanism, the degradation rate of MO can be elevated 3.5 times only by regulating the MO ratio in three states.