The present work prepared a copper N-heterocyclic carbene complex that could be used in catalyzing the homogeneous hydrogenation of carboxylic acid with ammonia borane (hydrogen source) to synthesize primary alcohols. Various aromatic and aliphatic carboxylic acids with diverse functional groups were transformed to respective alcohols in moderate to high yields. The process can be easily scaled up (TON up to 14545) and exhibit a high compatibility with different sensitive functional groups, including fluorine, chlorine, bromine, iodine, hydroxyl, cyano and nitro groups. IMesCuCl/NH3·BH3 combination can selectively reduce aromatic and aliphatic esters. Mechanistic studies indicate that Cu-H species produced in situ are the active intermediates.