The photoinduced semiconductor-to-metal transition (PSMT) unveils crucial photodynamic mechanisms and holds great promise for information storage, sensing, optoelectronics, optical switches, etc. All previously reported PSMTs have occurred between two structural phases of the same material, lacking real-space evidence at the atomic or molecular level. Herein, we report atomic-scale observations of a photoinduced 'face changing': light irradiation transforms a semiconductor copper selenide (Cu