Synchrotron-based angle-resolved photoemission spectroscopy is used to determine the electronic structure of layered SnSe, which was recently turned out to be a potential thermoelectric material. We observe that the top of the valence band consists of two nearly independent hole bands, whose tops differ by similar to 20meV in energy, indicating the necessity of a multivalley model to describe the thermoelectric properties. The estimated effective masses are anisotropic, with in-plane values of 0.16-0.39 m(0) and an out-of-plane value of 0.71 m(0), where m(0) is the rest electron mass. Information of the electronic structure is essential to further enhance the thermoelectric performance of hole-doped SnSe. (C) 2018 The Japan Society of Applied Physics