Abstract: Effect of ionic liquids (ILs) as media for the decomposition of formic acid in the presence of organic amine was investigated, and this activity was observed to be markedly promoted by the addition of ILs, especially for BMImCl. Based on this finding and to avoid volatile organic amine, a series of amine-functionalized ILs were further designed and prepared as both reaction media and cocatalyst for homogeneous decomposition of formic acid. Among the ILs investigated, i-Pr₂NEMImCl-HCOONa system exhibited high activity (TOF > 600mol/mol/h). This efficient and green method to produce hydrogen by formic acid decomposition has practical potentiality.