The ordered mesoporous MCM-41 materials incorporated with transition metal substituted polyoxometalate (PW11O39M1)5− (designated as M1–POM, M1=Ni2+, Co2+ or Cu2+) were synthesized via an original direct synthesis method. The samples were characterized by XRF, XRD, FT-IR, HRTEM, SEM and N2 adsorption isotherm techniques. The results show that M1–POM was uniformly dispersed in the samples and its structure remained intact in the materials. The samples exhibited excellent catalytic performance for the esterification of n-butanol with acetic acid, which is better than that of the supported lacunary polyoxometalate (PW11O39)7− and the impregnated (IM) samples.