Here, we demonstrate a facile synthesis of homogeneous Ag nanostructures fully covering the polyaniline (PANI) membrane surface simply by introducing organic acid in the AgNO(3) reaction solution, as an improved technique to fabricate well-defined Ag nanostructures on PANI substrates through a direct chemical deposition method [Langmuir2010, 26, 8882]. It is found that the chemical nature of the acid is crucial to create a homogeneous nucleation environment for Ag growth, where, in this case, homogeneous Ag nanostructures that are assembled by Ag nanosheets are produced with the assistance of succinic acid and lactic acid, but only scattered Ag particles with camphorsulfonic acid. Improved surface wettability of PANI membranes after acid doping may also account for the higher surface coverage of Ag nanostructures. The Ag nanostructures fully covering the PANI surface are extremely sensitive in the detection of a target analyte, 4-mercaptobenzoic acid (4-MBA), using surface-enhanced Raman spectroscopy (SERS), with a detection limit of 10(-12) M. We believe the facilely fabricated SERS-active substrates based on conducting polymer-mediated growth of Ag nanostructures can be promising in the trace detection of chemical and biological molecules.