In the present work, we first described the stable entrapment of the Superoxide ions in gamma-irradiated (Me4NOH + O-2) clathrate hydrate. Owing to peculiar direct guest-guest ionic interaction, the lattice structure of gamma-irradiated (Me4NOH + O-2) clathrate hydrate shows significant change of lattice contraction behavior even at relatively high temperature (120 K). Such Findings are expected to provide useful information for a better understanding of unrevealed nature (such as icy nanoreactor concept, ice-based functional material synthesis and lattice tuning by specific ionic guests) of clathrate hydrate fields.