In this paper, the liquid phase esterification of acetic acid with n-butanol was investigated over natural silica as a novel catalyst. The catalyst was characterized by XRF, XRD, and nitrogen sorption analysis. The effect of different parameters such as reaction time, molar ratio, catalyst dosage and calcination temperature on the esterification reaction was studied. The results show that, natural silica catalyst exhibited excellent catalytic performance with a selectivity of 100% to n-butyl acetate formation and the maximum yield obtained in batch method is 86%. This yield is successfully improved to a higher value nearly to 100% with a reactive distillation column.