The statues of active sites such as number and dispersion on the surface of support are essential to improve the catalytic activity. In this paper, highly-dispersed and controllable quantities of vanadia species within channel of mesoporous MCM-41 were directly prepared by a direct templating assembly method (S + L -M + I -). This method was based on the self-assembly of cationic surfactants (CTA + , S + ), chelating agents (citrate ions, L -), vanadyl ions (VO 2+ , M + ) and silicates oligomers (I -) by the electrostatic and chelating interaction. First, the citrate ions were absorbed on the CTA + micelles' surface by electrostatic interaction, the vanadyl ions subsequently were anchored on their surface by chelating with citrate ions to form metallomicelles. Finally, the silicates were deposited on the metallomicelles to obtain the targeted product. The structure of samples, especially the oxidation state and surface distribution of vanadium species on the mesoporous silica were efficiently characterized with different techniques including XRD, N 2 adsorption, SEM, TEM, UV-vis, XPS, FT-IR, ICP and H 2 -TPR.Furthermore, the obtained samples, using hydroxylation of benzene as a probe reaction, exhibited superior catalytic activities when compared with post-synthesized sample.