By using the characteristics of a hydrogen-absorbing alloy, the hydrogen produced by catalytic dehydrogenation of saturated compounds can be absorbed to form metal hydrides, and, vice versa, the resulting metal hydrides are able to hydrogenate efficiently unsaturated compounds upon dehydriding. Gas-phase reactions between 2-butene and 2-propanol on a hydrogen-absorbing alloy CaNi5 have been studied in the temperature range of 393-473 K. CaNi5 showed interesting characteristics as an active catalyst for the catalytic transfer hydrogenation of butene from propanol as a hydrogen donor. 2-propanol was effectively dehydrogenated at 423 K to yield acetone in which the dissociated hydrogen was completely absorbed by CaNi5 to form the metal hydride. When the alloy was hydrided to some extent, butene was hydrogenated by the absorbed hydrogen in the metal hydride to produce butane. The overall reaction on CaNi5 was expressed as catalytic transfer hydrogenation of 2-butene from 2-propanol through intermediate formation of metal hydrides, rather than the direct reaction between butene and propanol on the alloy. Thus, CaNi5 effectively repeated hydriding-dehydriding cycles: hydriding of CaNi5 by 2-propanol dehydrogenation with subsequent dehydriding for the hydrogenation of 2-butene. The use of hydrogen-absorbing CaNi5 provides a novel reaction system for the catalytic transfer hydrogenation.