Abstract: Poly(o-toluidine) (POT) with continuous 3D porous network structure was synthesized via self-assembly by interfacial polymerization with an assistance of phytic acid.The measurements of Scanning Electron Microscopy (SEM),nitrogen adsorption and contact angle had been used to investigate the microstructure,specific area and hydrophily of POT.Results indicate that when the concentration of phytic acid is 0.3 mol/L and the polymerization temperature is 10℃,POT exhibits 3D porous network structure with open channel size of 0.2~1 μm,and less than 200 nm polymer particles anchor on the surfaces of the networks.The POT shows relatively high conductivity (7.52×10^-3 S/cm) and specific area (37.5 m²/g) as well as good hydrophily (contact angle 34°).During the polymerization,the phytic acid with multiple functional-groups is used as the dopant and cross-linker,and its interaction with the polymer chains is the driving force for this self-assembly behavior.