Anionic clay pillared by triheteropolyoxometalates, ZnAl-XW11Co(X= Co, B or Ge),has been synthesized by ion exchange. The measurement results of XRD and IR confirm that the intercalation for XW11O39Co(H2O)n- takes place and results in gallery height of 0.99± 0.01um. The new pillared compounds are found to be efficient for esterification of acetic acid with n-butanol. It is found that the catalytic activityincreases as the negative charge of heteropolyoxometalates in ZnAlXW11Co decreases.