Pentamerous oligoaniline (POA) was protonated with sulfuric acid to form emeraldine salts (ES) and then intercalated in montmorillonite (MMT) CL120 to develop a functional conductive organo-layered material. The characteristics of the modified clay CL120/ES-POA were analyzed by wide-angle X-ray diffraction (WAXD) to find the d-spacing of the MMT layer distance, and by Fourier transform infrared (FTIR) spectroscopy for the oligoaniline functional group in CL120/ES-POA, and high-resolution thermogravimetric analysis (TGA) to determine the theoretical intercalation capacity of the modifying agent in the clay. We successfully intercalated the ES-POA into the MMT by ionic exchange reaction. Polymer-dispersed liquid crystal (PDLC) composites were prepared from the modified clay of 1 wt% loaded in the mixtures of 49 wt% photosensitive monomer and 50 wt% nematic liquid crystal (NLC), in a specific case, so as to generate novel functional nanocomposites. The hybridization of CL120/ES-POA clearly improved the electro-optical properties of the PDLCs. In this work, doping CL120/ES-POA at 1 wt% beneficially lowered the driving voltage by almost 70%, increased the transmission contrast ratio by five times and reduced the response time from 4.6 to 0.7 ms at 25 V rms at the expense of the viewing-angle properties.