A multi-reflection structure including a substrate and pyramid is provided. The substrate includes an inversed pyramid shaped recess having at least three first reflection sidewalls. The pyramid is disposed on the substrate and located in the inversed pyramid shaped recess. The pyramid has at least three second reflection sidewalls, wherein the normal of each of the second reflection sidewalls and the normal of each of the first reflection sidewalls are not located in the same plane. Furthermore, a photo-electric device is also provided in the present application.