lthough thermal expansion is a key factor in relation to the host guest interaction of clathrate hydrates, few studies have investigated the thermal behavior of ionic clathrate hydrates. The existence of ionic species in these hydrates creates a unique host guest interaction compared. to that of nonionic clathrate hydrates. It was revealed that X-ray diffraction cannot be used for research of tetramethylammonium hydroxide clathrate hydrates due to damage of the cations by the X-ray, which results in abnormal thermal expansion of the ionic clathrate hydrates. Hence, in the pres-ent work, the thermal expansivities of binary sII Me(4)NOD - 16D(2)O and sI DClO(4) center dot 5.5D(2)O were measured by neutron powder diffraction (NPD) in order to shed light on their thermal behavior. General correlations for the thermal behaviors of given structures were established and lattice expansions depending on the guests were compared between ionic and nonionic clathrate hydrates. The peculiar change in the thermal expansivity of binary DClO(4) center dot 5.5D(2)O was also considered in relation to the host guest configuration.