A novel initiator-assisted polymerization is used for bulk synthesis of polypyrrole (PPy) nanoparticles by adding a catalytic amount of initiator 2,4-diaminodiphenylamine into pyrrole solution. Through simply modulating reaction parameters such as initiator concentrations, oxidant species, oxidant/monomer molar ratios and acidic media utilized, the chemical structure, nanomorphology, product yield, dispersibility, thermal stability, electrochemical activity, and conductivity of PPy nanoparticles are facilely optimized. The initiator copolymerized with pyrrole in the initial stages of polymerization, acting like bipyrrole and helping to nucleate the PPy main chains. The stronger oxidants and higher oxidant/monomer molar ratios used lead to PPy nanoparticles with higher pi-pi conjugation. Sphere-like PPy nanoparticles with average diameters of 80-300 nm show yield and conductivity with values up 73.5% and 10(-2) S/cm, respectively, and are readily dispersible in both water and N-methylpyrrolidone. The PPy nanoparticles are used as effective precursors for fabricating carbon nanoparticles with conductivity of 3.7 S/cm. Nanocomposite membranes consisting of PPy nanoparticles and polysulfone matrix are fabricated by a phase-inversion technique and demonstrate much improved hydrophilicity, water permeability, and bovine serum albumin selectivity against pure polysulfone membranes. Crown Copyright (c) 2012 Published by Elsevier Inc. All rights reserved.