Hydrogen molecules are known to occupy the small cages of structure I (sI) and II (sII) hydrates with the aid of coguests, leading to the highly stable state of their crystalline framework. For the first time, we synthesized the double hydrogen hydrates incorporated with ethane and propane that play a special role as the hydrate promoters or stabilizers. The resulting hydrate structures cage occupancy was identified by the spectroscopic methods of the PXRD and solid-state NMR. In addition, direct GC analysis confirmed that the encaged hydrogen amounts are 0.127 for sI ethane and 0.370 for sII propane at 120 bar and 270 K. The proper hydrate thermodynamics particularly focusing on the cage occupancy estimated that 0.17 and 0.33 wt% of hydrogen are observed in small cages of sI and sII hydrates. The overall spectroscopic and physicochemical analysis strongly imply that the sII cages act as much more favorable sites than sI cages in storing hydrogen.