A series of copper-doped mesoporous silica pillared clay (Cu-MSPC) with high catalytic performance on the hydroxylation of benzene to phenol have been synthesized with a facile process. The high conversion (31.1%) and selectivity (96%) toward phenol are achieved with only 4.16% copper loading. The characterization results show that the copper of these materials is doped in the intergallery silica pillar, leading to the high catalytic performance at low copper loadings. Meanwhile, the formation of Cu-MSPC structure is proposed.