<jats:title>Abstract</jats:title><jats:p>Three different tailored mesostructured hybrid organic‐inorganic materials containing single site Ir–NHC moieties (NHC = N‐heterocyclic carbene) were synthesized by a very convenient and attractive methodology: (i) the synthesis of mesostructured materials with different pore‐sizes and containing two types of imidazolium units regularly distributed along their channel pores was achieved using a sol‐gel process via a templating route; (ii) the in situ transformation of the imidazolium moieties to Ag–NHC units was quantitatively performed; (iii) the transmetallation of Ag–NHC groups with [Cp*IrCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub> was carried out successfully. Each step was controlled fully and evaluated by several analytical techniques (XRD, N<jats:sub>2</jats:sub> adsorption, elemental analysis, and solid state NMR). The catalytic properties of the resulting Ir–NHC‐containing materials were studied in H/D‐exchange reactions with various substrates, and compared to their homogeneous homologues. Their catalytic activity highlighted the following: (i) the substituents on the NHC ring have an important role; (ii) the size of the pores have no influence on the catalytic reactivity; (iii) the close environment around the metal center has a major influence on the catalytic reaction. This latter point suggests that the selective C–H bond activation by mesoporous catalysts with a mixture of reagents can be performed by fine tuning the steric hindrance around the metal centers, while keeping big pores for easy of diffusion of substrate and product molecules.</jats:p>