Basic catalysts for carbon–carbon addition reactions were synthesized by immobilization of amine species on silica supports. Tetraethylenepentamine was impregnated and immobilized on amorphous silica (SiO2) and SBA-15 using an epoxy resin. The basicity of the catalysts was determined by adsorption–desorption of CO2 and the degree of immobilization was evaluated by FTIR. The catalytic activity towards the Claisen condensation reaction of methyl benzoate and methyl ethyl ketone was evaluated by an in-situ FTIR micro-scale reactor. A mechanism is proposed to show that the catalysts promote the formation of β-diketone and methanol; the effects of the support and amine immobilization degree are discussed.