In this work, a coating method was used to prepare a liquid crystal physical gel with a high orientation of liquid crystal molecules, excellent electrical conductivity, and mechanical stability. The liquid crystal matrix used was nematic phase liquid crystal (5CB), the gel factor was polyvinyl alcohol (PVA), and the conductive filler was carbon nanotubes/polyaniline (CNT/PANI). Chemical in situ polymerization was used to create CNT/PANI composites, wherein polyaniline encapsulates the carbon nanotubes to enhance their dispersion. At 4 mm/s, 7.2 N of coating pressure, and 72 s of interval duration, the shear flow-induced orientation was achieved. The consistent and large-area orientation of the liquid crystal molecules was realized and the orientation direction of the liquid crystal molecules was parallel to the coating direction. Additionally, a type of stress sensor assembly based on multiple coating demonstrated a good sensor performance in the 90° bending test and high sensitivity in the 20% tensile test, with a sensor sensitivity of 23.25. Regarding the use of liquid crystal materials in flexible electronic devices, it is quite important.