A mesoporous MnO2/C composite was prepared by impregnating self-made porous carbon spheres with manganese nitrate aqueous solution and subsequently reacting with KMnO4 aqueous solution. It was characterized with X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), the Brunauer-Emmett-Teller (BET) surface area and the Barrett-Joyner-Halenda (BJH) pore size distribution. The as-prepared mesoporous MnO2/C composite was used as catalyst for the synthesis of n-hexyl acetate, and the effects of MnO2 loading and esterification reaction parameters on the esterification rate were investigated. The results prove that MnO2 loading has a significant effect on the catalytic activity and that the mesoporous MnO2/C composite exhibits high catalytic activity with an esterification rate of 96.42% under the conditions below: MnO2 loading (73.09 wt%), catalyst dosage (0.1% in total weight), acetic acid/n-hexanol molar ratio (2:1), reaction temperature (130 degrees C) and reaction time (5 h). (C) 2012 Elsevier B.V. All rights reserved.