Mesoporous silicas functionalized with the L-prolinamide group in the mesopore were synthesized by co-condensation of silicon precursors with L-prolinamide modified organosilane (PCA) in HOAc-NaOAc buffer solution (pH = 4.4) using block copolymer P123 as a template. The highly ordered 2D hexagonal mesostructure was obtained through one-pot co-condensation of tetraethoxysilane (TEOS), Na2SiO3 and PCA as silicon source. The disordered foam-like mesostructure was also obtained when TEOS and PCA were used as silicon sources. In asymmetric aldol reaction of cyclohexanone with 4-niti-obenzaldehyde, the materials with highly ordered mesostructure exhibit higher enantioslectivity (91% ee) than that with disordered foam-like mesostructure (75% ee), suggesting that the ordered pore structure imparts improved enantioselectivity. The L-prolinamide functionalized materials were also synthesized by grafting PCA onto mesoporous silicas. which showed catalytic efficiencies similar to the materials synthesized by the co-condensation method. (C) 2009 Elsevier B.V. All rights reserved.