The high-pressure technique is a fundamental tool for realizing novel phase transitions, chemical reactions, and other exotic phenomena. Hydrogenation is one example of a high-pressure reaction; at high pressures of several gigapascals, hydrogen becomes chemically active and reacts with metals and alloys to form hydrides. This paper covers a high-pressure study of the hydrogenation process and the synthesis of hydrides using a cubic-type multi-anvil apparatus. The experimental details of a hydrogenation cell assembly, high-temperature and highpressure generation, and an in situ observation technique are presented. These experiments are conducted with the aid of in situ synchrotron radiation X-ray diffraction measurements operated in an energy-dispersive mode in the conventional manner for time-resolved measurements and a newly developed angle-dispersive mode for observation of the crystal growth process during formation of metal hydrides. Two successful cases of high-pressure hydrogenation are presented: aluminum hydride, Al H3, and an aluminum-based alloy hydride, Al2 Cu Hx, which are potential candidates for hydrogen storage materials. The high-pressure technique is a fundamental tool for reproducing novel phase transitions, chemical reactions, and other exotic phenomena. Hydrogenation is one example of a high-pressure reaction; at high pressures of several gigapascals, hydrogen becomes chemically active and reacts with metals and This paper covers a high-pressure study of the hydrogenation process and the synthesis of hydrides using a cubic-type multi-anvil apparatus. The experimental details of a hydrogenation cell assembly, high-temperature and high-pressure generation, and an in situ observation technique are presented. These experiments are conducted with the aid of in situ synchrotron radiation X-ray diffraction measurements operated in an energy-dispersive mode in the conventional manner for time-resolved measurements and a newly developed angle-dispersive mode for observation of the crystal growth process during formation of metal hydrides. Two successful cases of high-pressure hydrogena are presented: aluminum hydride, Al H3, and an aluminum-based alloy hydride, Al2 Cu Hx, which are potential candidates for hydrogen storage materials.