A preparing process of a chitosan/polyvinyl alcohol composite nanometer electrically-conductive fiber is disclosed. The process includes a step of adding 50 mL of an aqueous solution of glacial acetic acid and 0.1 g of nanometer graphite powder into a three-necked flask, dissolving the nanometer graphite powder to obtain a mixture solution, performing ultrasonic dispersion for 1.5-2.5 h, then adding 1 g of chitosan particles, and stirring the mixture with an electric stirrer for 3 h to obtain a chitosan/polyvinyl alcohol spinning solution; a step of adding the prepared spinning solution into an injector having a volume of 20 mL in a plurality of times, fixing the injector to a high-voltage static spinning device, and connecting the metal needle head of the injector to one pole of a high-voltage power source; a step of cladding a receiving plate with a layer of an aluminum foil receiving plate connected to the other pole of the high-voltage power source, setting the spinning voltage, the receiving distance and a pushing speed, spinning, adding the obtained composite nanometer fiber into an aniline monomer solution for 2-2.5 h, taking the fiber out, and uniformly extruding the fiber, with the liquid carrying rate being controlled to within a range of 110-120%; a step of adding the obtained composite nanometer fiber adsorbing the aniline monomer into a reaction liquid for 1.5-2 h; and a step of taking the fiber out, washing the fiber with deionized water and naturally drying the fiber in wind to obtain a finished product.