Catalytic esterification of acetic acid with iso-amyl, benzyl, and cinnamyl alcohols in the liquid phase over unmodified natural silica catalyst has been studied. The virgin and calcined catalysts were characterized by thermal analyses (Thermogravimetry (TG) and diffrential thermal analysis (DTA)), X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier transform infrared (FTIR), scanning electron microscope (SEM), and N₂ sorption analyses. The acidity of natural silica catalysts was investigated using isopropyl alcohol dehydration and chemisorption of pyridine and dimethyl pyridine. The results indicated that most of the acidic sites are of Brϕnsted type and of intermediate strength. The effect of different parameters such as reaction time, molar ratio, catalyst dosage, and calcination temperature was studied. Natural silica catalyst exhibited excellent catalytic performance with a selectivity of 100% to acetate esters formation. The maximum yields of isoamyl, benzyl, and cinnamyl acetate esters obtained in the batch conditions were 80, 81, and 83%, respectively. Whereas on adopting a simple distillation technique, these yields were successfully improved to higher values of 97, 98, and 90%, respectively. Experimental results manifested that the reaction followed Langmuir–Hinshelwood mechanism. Finally, the catalyst could be completely recycled without loss of its activity after four cycles of the esterification reactions.