Gas hydrates are solid crystal structures formed by enclathration of gaseous guest species into 3-dimensional lattice structure of hydrogen-bonded water molecules. These compounds can be potentially used as an energy storage/transportation medium because they can hold a large amount of gas in a small volume of the solid phase. In addition, huge amount of natural gas, buried in seabeds or permafrost region in the form of the solid hydrate, is regarded as a future energy source. In this study, synthesized natural gas, whose composition is 90.0 mol% of methane, 7.0 mol% of ethane, and 3.0 mol% of propane, was used to identify formation behaviors of natural gas hydrates for the purpose of applying the gas hydrate to a storage/transportation medium of natural gas. According to the experimental results obtained by means of the solid-state NMR and high-resolution powder XRD methods, it is found that formed natural gas hydrates have crystal structure of the structure-II hydrate, and that methane occupies both small and large cages, while the others only occupy large ones. In addition, both the NMR spectroscopy and the gas chromatograph showed that there exists preferential occupation among the natural gas components during the hydrate formation. Compositional changes after the hydrate formation revealed that the preferential occupation is in order of propane, ethane, and methane (propane is the most preferential guest species when forming natural gas hydrates).