The ordered mesoporous material SBA-15 (FCSBA-15) with an enhanced hydrothermal stability was successfully synthesized from natural kaolin in the presence of a fluorocarbon surfactant. FCSBA-15 was further used as the support for Fe/BiOCl with the aim of exploring its Fenton-like catalytic performance toward the degradation of 2-nitrophenol. Based on characterization techniques including X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), no phases referring to the Fe species were observed, suggesting that the Fe³⁺ ions may be present on the surface of flower-like BiOCl. It is noted that the Fe³⁺ ions could lead to a morphological reconstruction from BiOCl nanosheets to BiOCl flowers. The obtained Fe/BiOCl–FCSBA-15 exhibited an excellent degradation efficiency for 2-nitrophenol, which reached nearly 100% within 40 min by optimizing parameters such as the H₂O₂ dosage, pH value, temperature, Fe/Bi molar ratio and Bi/Si molar ratio. The finding reported here is important and may help to develop novel mesoporous matrix based systems for advanced catalysts.