New inorganic 2D framework of H2[{La3(H2O)21}P2W18Ce3O70(OH)(H2O)3]•24H2O (La3P2W18Ce3) and Cu [{La3(H2O)21}P2W18Ce3O70(OH)(H2O)3] (CuLa3P2W18Ce3) were synthesized and characterized by FT-IR, X-ray single-crystal diffraction, PXRD, FESEM-EDX and Uv-Vis spectroscopy. The X-ray single-crystal diffraction revealed that La3P2W18Ce3 structure consist of Ce4+ sandwiched A-type polyoxometalate which connected together via different aqua coordinated La3+ ions to form a 2D inorganic framework. The insoluble Cu2+ de- rivative, CuLa3P2W18Ce3 was synthesized by addition of Cu2+ acetate salt to the La3P2W18Ce3 sparingly soluble. The as-synthesized inorganic frameworks were used as heterogeneous catalysts to promote the synthesis of α-acyloxy amides via the well-known Passirini reaction and synthesis of bis-amides via the well-known Ugi under mild conditions.