A facile approach to the formation of Ag/PPy composite film, through the reaction of Ag+ and pyrrole monomer, was developed with the help of synergistic effect of NH3 center dot H2O on this reaction. Black or gray Ag/PPy film precipitated on the insert wall of the vessel within 0.5 h with this new method. The Ag/PPy composite film has good conductivity (sheet resistance: 0.28 Omega/square) and superhydrophility (contact angle of water, CAW similar to 0 degrees). Mechanism involved in the reaction rate acceleration was briefly discussed. (C) 2009 Elsevier B.V. All rights reserved.