Cuprous oxide (Cu2O) crystals are usually used as the photocatalysts of water splittings and carbon monoxide oxidations. Herein, we report the new catalytic properties of Cu2O to the electrochemilumenescence (ECL) reactions of luminol and oxygen. Adjusting the shape of Cu2O microcrystals from cube to octahedra also facilities the improved electrocatalytic acticity, where octahedral Cu2O microcrystals possess higher ECL signal by 25% at -0.6 V (versus Ag/AgCl) at pH 7.4. The octahedral Cu2O microcrystals are synthesized by the coordination of iodide ions to the surface, which alters the crystals shapes from cubes to octahedra. Size-distribution of octahedra is improved with this mehod compared to the previous studies with only hydroxide ions as the coordinates. The catalytic activity of octahedral Cu2O crystals is expected to be compared with the noble metal nanomaterials and constructed the high-efficiency and low-cost ECL biosensors.