N-Phenylpyrrolidine was efficiently synthesized over the mesoporous Al2O3 catalyst by the reaction of the aniline and 1,4-butylene-glycol at atmospheric pressure. The catalyst exhibited very high activity and selectivity. At the reaction temperature of 300℃, 1,4-butylene glycol conversion attained 100% and the selectivity of N-phenylpyrrolidine could exceed 98%.