A new cerium polyoxomolybdate {[Ce(H2O)7Al(OH)6Mo6O18]·4H2O} (compound 1) was synthesized and characterized by X-ray diffraction analysis, elemental analysis, TG analysis and IR spectrometry. Compound 1 exhibits a zigzag chain-like structure, which is constructed from an Anderson type anion and rare earth metal, Ce (Ⅲ).These 1-D chains are further extended into a 3-D network by the aid of multipoint hydrogen-bonding interactions.