The first-time use of the oxazaborolidine complex in transfer hydrogenation was accomplished. It was prepared without difficulty from cheap materials: ethanolamine and BH·THF. A general and efficient method for copper-catalyzed transfer hydrogenation of a variety of N-heteroaromatics with an oxazaborolidine-BH complex under mild reaction conditions afforded the corresponding hydrogenated products in up to 96% yield. Mechanistic studies indicate that the hydrogen source originated from water and borane that coordinate with the nitrogen atom of oxazaborolidine. Accordingly, a plausible mechanism for this reaction was proposed. This method was successfully used in the key step synthesis of natural products (±)-angustureine and (±)-galipinine in three steps.