A facile method has been developed to incorporate FeOx into the channels of anionic surfactant‐templated mesoporous silica (AMS). This synthesized method was based on a novel templating route (S−[MN]+I−), in which Sar‐Na (N‐Lauroylsarcosine sodium) was employed as structure‐directing agent (S−), Fe ion functionalized APATES (N‐[3‐(Trimethoxysilyl)propyl]ethylenediamine) as co‐structure directing agent ([MN]+). The Fe ion functionalized APATES (Fe[APATES]+) could establish a critical interaction between the surfactant head group and silica species by counterion‐mediated interaction during the synthesis process. The synthesized samples were characterized with XRD, N2 adsorption, XPS, FT‐IR, UV‐vis, H2‐TPR, TEM. The results revealed that FeOx species could be highly dispersed onto the pore channel surface and have a strong interaction with the silica wall. Furthermore, this catalyst of FeOx‐AMS exhibited high catalytic performances for the hydroxylation of phenol.