Siliceous mesostructured cellular foams （MCFs） are a new class of three-dimensional hydrothermally robust materials with ultralarge mesopores. The open system of large pores and the controllable pore size give MCFs unique advantages as catalyst supports. In this paper, MCFs were employed as supports in developing the PPh3-Rh/MCF catalyst for propylene hydroformylation in a fixed-bed reactor. The PPh3-Rh/MCF catalyst shows high activity （propylene conversion of 21.6% and butyraldehyde TOF of 160.6 h -1）, high selectivity （n-butyraldehyde/i-butyraldehyde=10.4）, and excellent stability under mild conditions of p=1.0 MPa, T=393 K, and SV= 2?000 h -1.
