A new kind of multilayer Trims containing 1:12 molybdosilicate acid (SiMo12) anions was achieved on the surface of gold electrode by alternate deposition of 1 : 12 molybdosilicate acid with polydiallyldimethylammonium chloride (PDDA). The electrochemical behavior of the multilayer films was described in detail. The chemically modified electrode (CME) was shown to exhibit an excellent electrocatalytic activity toward the reduction of nitrite ions in 0.5 M sulfuric acid and possesses several attractive features, such as simple preparation, fast response, good chemical and mechanical stability, and independence of electrode size and topology.