A facile and novel strategy for preparing polyaniline/polyvinyl alcohol (PANI/PVA) composite emulsion is reported wherein the reaction is carried out via the emulsion polymerization using ammonium peroxydisulfate (APS) as the oxidizing agent and dodecylbenzene sulfonic acid (DBSA) as the protonic acid. The PANI/PVA composite membranes have been characterized using optical microscope, scanning electron microscope (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and electrochemical workstation. It is interesting that the electrical conductivity of the PANI/PVA composites is estimated to be as high as 1.28 S/cm. The experimental results show that the surface of PANI/PVA composite membranes exhibits good integrity. The PANI particles at the nanoscale are dispersed in the PVA matrix, and the electrochromic behaviors of PANI/PVA composites obtained at different polymerization temperatures can be compared based on cyclic voltammetry (CV) curves, revealing that PANI/PVA composites synthesized at room temperature are better than those synthesized at low temperature.