The Keggin-type Cs2.5H0.5PW12O40 was encapsulated in metal-organic framework UiO-66 by a simple solvothermal synthesis method. The characterization results showed that the morphology and crystal structure of UiO-66 were preserved, and the heteropolyanion structure remained unchanged after Cs2.5H0.5PW12O40 encapsulation. The prepared Cs2.5H0.5PW12O40@UiO-66 material has demonstrated to be an environmentally benign catalyst in the acidolysis of soybean oil with medium-chain fatty acids for the production of low-calorie structured lipids. The FT-IR CO adsorption experiments revealed that additional Lewis acid sites were formed in the solid acid catalyst, which were essential to catalyze the acidolysis reaction. The solid catalyst could be reused for several recycles without obvious deactivation due to hardly leaching of active components into the reaction mixture.