In the present study, a novel solid acid catalyst based on titanium dioxide (2.5-10 wt %) supported on natural phosphate (TiO2/NP) was prepared by a sol-gel process, and 10 wt % loaded catalyst was characterized by several physicochemical techniques. The performances of the synthesized catalyst were investigated in esterification of oleic acid with methanol. The catalytic performance was screened under different reaction conditions, namely, loading amount of TiO2, calcination temperature, molar ratio of methanol to oleic acid, reaction temperature, and amount of catalyst. Under optimal conditions, the catalyst loaded with 10 wt % TiO2 and calcined at 800 C showed the highest oleic acid conversion of 87%. The catalyst showed a good stability under high reaction temperature and can be reused without severe loss of activity. As a versatile application, the TiO2(10)/NP catalyst exhibits a good ability for the esterification of free fatty acids in a highly acidic feedstock.