A direct preparation of polyaniline solution from aniline monomer is carried out by: adding aniline monomer, water, emulsifier, organic solvent in certain ratio into a reactor, stirring fiercely to form emulsifying liquid, controlling reactive condition, adding oxidant to make emulsifying liquid after reaction finished, adding an emulsion breaker to produce a uniformity solution, settling to separate, removing water-phase, washing and separating, removing organic-phase solvent partly or completely through evaporation to obtain different concentration polyaniline or solid polyaniline. The polyaniline solution prepared by above method has excellent electrochemical performance and chemical stability, controllable conductivity. The synthesis is simple, and can be used in photoelectron appliance, transducers, molecular wires, and molecular appliance, electromagnetic shielding materials, metal anti-corrosion and stealth technology.