Carbon nanotubes paste (CNTP) electrode was prepared with multi-walled carbon nanotubes and methyl silicone oil. Polyoxometalates (POMs) were assembled on the electrode surface with different methods, and investigated by cyclic voltammetry and Raman spectroscopy. Experiments showed that POMs/CNTP electrode prepared by direct method had better performance. K 6 P 2 Mo 18 O 62 ·14H 2 O (P 2 Mo 18 ) assembled CNTP electrode (P 2 Mo 18 /CNTP) electrode possessed good reversibility and could catalyze the reduction of bromate and iodate in 0.1M H 2 SO 4 solution. Further, the multilayer films of P 2 Mo 18 assembled CNTP electrodes were fabricated by layer-by-layer technique, which showed higher electrocatalytic activities. All these POMs assembled CNTP electrodes prepared exhibited good stability.