Sulfonated-p-cresol (SPC) was used as novel dopant for the first time in the synthesis of polyaniline in 3D nanofiber networks (PANI-3D). Polyaniline in 3D nanofiber network was prepared using organic solvent soluble benzoyl peroxide as oxidizing agent in presence of SPC and sodium lauryl sulfate (SLS) surfactant via inverted emulsion polymerization pathway. The influence of synthesis conditions such as the concentration of the reactants, stirring/static condition, and temperature etc., on the properties and formation of polyaniline nanofiber network were investigated. Polyaniline in 3D nanofiber network with 40-160 nm (diameter), high yield (134 wt % with respect to aniline used), and reasonably good conductivity (0.1 S/cm) was obtained in 24 h time. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120: 2421-2427, 2011