This study used a photo-reduction method to investigate cuprous oxide (Cu2O) self-assembled micro/nanostructures, and design a test specimen with an electron concentration gradient distribution. It also observed the Cu2O reduction of the self-assembled structure with respect to electron density. SEM analysis was adopted to analyze the growth mechanism and growth model. The results showed that, its structure size increased with photo-reduction time, and as the reduction solution concentration increased, its structure crystallinity declined. The basic unit of a self-assembled microstructure was Cu2O at a diameter of 10~15nm, then these particles conglomerate in self-assembly to form various kinds of Cu2O micro/nanostructures with respect to reduction electron density, and primarily presented in the form of a cone or cube. In the process of continuous self-assembly, there were many micro-defects under the perfect crystal surface. Considering the growth rate, the final growth surface of the structure was (111) or (100).