A new organic–inorganic hybrid silica material derived from a bis-silylated prolinamide by sol–gel methodology has been successfully applied as a supported organocatalyst in asymmetric aldol and Michael reactions. Our immobilized system presents similar performances to homogeneous prolinamides and added advantages of easy recovery and good recyclability. It fits green chemistry requirements as the reactions are performed in water, at room temperature, with low catalyst loadings (2–16 mol%).