Hybrid lead halide perovskite possesses attractive properties and outstanding performance. The electronic structure of hybrid lead halide perovskite single crystal can be used to comprehend its intrinsic properties. In this study, the crystal structure of CH3NH3PbBr3 perovskite crystal was elucidated by transmission electron microscopy. Phonon modes and CH3NH3+ rocking modes were analyzed. Band gaps of the crystal were obtained by temperature-dependent Raman scattering spectroscopy and photoluminescence measurement. Surface potential measurement for a (001) plane exhibited a work function of the material and other phases of PbBr2 and CH3NH3Br. From experimentally determined values, an electronic structure of CH3NH3PbBr3 was built. It showed a p-type characteristic.