An acid activated montmorillonite, treated with organic cationic surfactant, i.e. cetyltrimethylammonium bromide (CTAB), was used as a template to prepare TiO2 pillared montmorillonite taking titanium ethoxide as titania precursor in hydrochloric acid environment. The pillared montmorillonite was further promoted by dodecatungstophosphoric acid impregnation. The as prepared materials were characterized by various spectroscopic and analytical characterization techniques. The catalyst was employed towards a solvent free esterification of acetic acid with n-butanol. The catalyst showed excellent results with 88% conversion and 100% butyl acetate selectivity. It can be recovered and reused readily, making product isolation and catalyst reuse simple.