Abstract: In this paper, the preparation and Temperature Coefficient of Resistance (TCR) characteristic of nano-VO2 powder/Poly(3,4-ethylenedioxythiophene) composite is described. A simplified model of equivalent resistance of the composite was given and the results of calculation showed that the structure of series resistance leaded to the Negative Temperature Coefficient (NTC) characteristic of the composite, which was owned by the high resistance ingredient of the composite. The test results of resistance showed a change of above one order of magnitude due to the cooperation of the doped nano-VO2 powder and the electrical conductivity of poly(3,4-ethylenedioxythiophene). The surface morphology of films were studied by scanning electron microscope.