The prepared composite photocatalyst H3PW12O40/TiO2 was synthesized by sol-gel impregnation method and characterized by scanning electron microscope(SEM), energy-dispersive X-ray spectroscopy(EDS), Fourier transform infrared(FT-IR), X-ray diffraction(XRD), UV-vis diffuse reflectance spectrum(DRS) to investigate its optical, physical and chemical properties. The results indicated that the modified catalyst was coated with P and W element, still have uniform anatase structure. Meanwhile, there is a chemical interaction exists between the Keggin unit and the surface of the titania matrix. Compared with original H4PW12O40 or TiO2 matrix, the adsorption threshold onset of the composite extended to the visible region. Effects of H3PW12O40/TiO2 dosage, pH value, initial p-NA concentration on the photocatalytic degradation of p-NA under 250W UV irradiation were investigated. The optimal H3PW12O40/TiO2 dosage and pH value for degradation of 10mg/L p-NA were o.6g/L and 3.0, respectively. The degradation rate of p-NA by H3PW12O40/TiO2 process could be fitted pseudo-first-order kinetics. Moreover, 66% degradation of p-NA was still observed in the 5th recycle experiment. Futhermore, 4-Aminophenol, Phenol, Hydroquinone, 4-Benzoquinone and other intermediate products were indentifieded by GC/MS and a possible reaction mechanism is proposed on the basis of all the information obtained from the analysis of FT-IR and the above intermediates.