Novel architectured porous Cu@Cu2O hybrid microspheres were successfully designed and synthesized using silk sericin (SS) as structure-director to firstly form the hierarchical Cu2O/SS microspheres by self-assembly, followed by a calcination process. A possible mechanism has been proposed based on the results of FESEM, TEM and XRD analysis. The photocatalytic performance of obtained porous Cu@Cu2O hybrid microspheres was investigated, and the synergistic effect of Cu and Cu2O phases contributed to improving the light absorption ability, electron-hole separation and transfer compared with pure Cu2O. Importantly, the photo-degradation ratio of Cu@Cu2O hybrid microspheres for methyl orange (MO) reached up to 99.9% after 110 min visible light irradiation, which is almost 1.3 times than that of pure Cu2O. Furthermore, Cu@Cu2O hybrid microspheres also exhibited outstanding reusability and stability because that its degradation efficiency for MO still maintained at 93.5% after five cycles.