The room temperature synthesis of copper (Cu) nanoparticles (NPs) supported within SiO2 mesoporous thin films (MTF) modified with either COOH or NH2 functional groups is reported. The functional groups present in the MTF surface acted as adsorption sites for Cu (II) ions, which were afterwards reduced to Cu NPs in presence of sodium borohydride at room temperature. The oxidation state of the copper NPs, corroborated by X-ray Photoelectron Spectroscopy and Electron Energy Loss Spectroscopy, was strongly dependent on the functional group present in the pores of the MTF and on the number of adsorption/reduction (A/R) cycles applied for NPs loading. Metallic Cu (0) NPs were obtained in MTFs displaying COOH groups applying 10 A/R cycles while NPs with higher oxidation state were as well present after 20 A/R cycles. For MTF functionalized with NH2 groups the copper is present as Cu (I) and Cu (II) in the NPs but no Cu (0) can be detected. The MTF-Cu(CuOx) composite materials were tested as catalysts for the reduction of 4-nitrophenol in the presence of NaBH4. Catalytic activity of composite materials depends on the oxidation state of Cu NPs, being more active those samples containing Cu (0) NPs, synthesized from COOH functionalized MTFs.