Well-ordered hexagonal mesoporous silicate (HMS) materials with various contents of phosphotungstic acid (HPW) were synthesized via an original direct synthesis method. The characterization results show that the samples have regular fingerprint-like mesopores and spherical morphology. Compared with the conventional wet impregnation method, the samples obtained by the original direct synthesis method have better HPW dispersion and larger specific surface area. Finally, the catalytic performance of these samples was tested through the oxidative desulfurization (ODS) of DBT in the model oil. The results indicate that the direct synthesized samples exhibit better catalytic performance than the impregnated samples.