The chemical oxidation polymerization of m-phenylenediamine (MPD) by ammonium persulfate (APS) at room temperature results in the formation of poly(m-phenylenediamine) (PMPD) microparticles. The subsequent treatment of such microparticles with an aqueous AgNO(3) solution produces Ag nanoparticle (AgNP)-decorated PMPD microparticles. It was found that as-formed AgNPs exhibited remarkable catalytic performance toward the reduction of hydrogen peroxide (H(2)O(2)). The enzymeless H(2)O(2) sensor constructed with such composites showed a fast amperometric response time of less than 5 s, and the corresponding linear range and detection limit were estimated to be from 0.1 to 30 mM and 4.7 µM, respectively, at a signal-to-noise ratio of 3.