A series of silver-modified phosphotungstic acid catalysts AgxH3-xPW12O40 (x=1, 2, 3) were synthesized by incorporating silver nitrate into phosphotungstic acid. The structure, stability and acidity of the catalysts synthesized were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermal gravimetric analysis-derivative thermogravimetric analysis (TGA-DTG) and 31P-TMPO magic-angle spinning nuclear magnetic resonance (31P-TMPO MAS-NMR) spectroscopy. The effects of various reaction parameters, such as methanol/oil molar ratio, amount of catalyst, reaction time, and reaction temperature on the catalytic transesterification of soybean oil and methanol with Ag2HPW12O40 were investigated. The results demonstrated that Ag2HPW12O40 had the best catalytic activity, superior biodiesel yield and excellent durability. The high catalytic activity of the catalyst was attributed to Brønsted-Lewis acid synergy. With 6 wt.% Ag2HPW12O40 catalyst, the yield of biodiesel reached 96.4% with a methanol/soybean oil molar ratio of 32/1, a reaction temperature of 150℃ and a reaction time of 20 h.