In this paper, we report a clever approach permitting, in one step, the synthesis of ordered (hexagonal phase) mesoporous silica functionalized with iodopropyl groups [I(CH₂)₃] located in the pore channels. This material was obtained by the hydrolysis and co-condensation of tetraethylorthosilicate (TEOS) and iodopropyltriethoxysilane (I(CH₂)₃Si(OEt)₃) in the presence of P123 as a non-ionic structure-directing agent and hydrogen iodide as an acid catalyst. All materials were characterised by X-ray diffraction measurements, transmission electron spectroscopy, nitrogen adsorption analyses, elemental analyses, and solid-state ¹³C and ²⁹Si NMR spectroscopy. The accessibility and reactivity of this functional group was investigated, showing the advantage of the iodo group for the introduction of bulky or hydrophilic groups.