This paper reports the (13)C NMR characterization of functionalized MCM-41's and describes the chemistry that occurs in the pores of these materials in the process of forming gold nanoparticles. Nanoparticles formed on hexagonal mesoporous silica (MCM-41) by hydrogen reduction of chloroauric acid have little affinity for pure silica surfaces. The gold can be removed from the support with very mild treatment, for example, solvent extraction. The loss of gold from the substrate can be prevented using a pore functionalization methodology that entails synthesis of the silica containing polydentate amine functionality chemically bound in the mesopores. The synthetic scheme introduces solvents and templating reagents (surfactants) into the mesopores that are chemically reactive under the conditions required for gold particle formation. Extensive base-catalyzed elimination and nucleophilic substitution reactions involving the tetraalkylammonium surfactant occur during the reduction of chloroauric acid to gold.