In contrast to the structural studies of laboratory-grown gas hydrate, this study has been performed on naturally grown clathrate hydrates from the sea floor. The PXRD pattern of natural gas hydrate shows that the sample had a structure I hydrate. The 13C NMR spectrum was obtained for the natural gas hydrate sample in order to identify the cage occupancy of guest molecules and determine the hydration number. The NMR spectrum reveal that the natural gas hydrates used in this study contain only methane with no noticeable amount of other hydrocarbons. The existence of two peaks at different chemical shifts indicates that methane molecules are encapsulated in both large and small cages. In addition, Raman spectroscopic analysis is also carried out to identify natural hydrates and compared with the NMR results. Investigating the composition and structure of natural gas hydrates is essential for applying natural gas hydrates as a novel energy source.