Efficient energy storage is becoming a serious niche area nowadays due to exponential growth in energy consumption. Different approaches have been developed and implemented to improve the performance of the devices, in which improving conductivity is a major issue. In the present work, cotton fabric was converted into a conductive material by incorporating graphene, using the Layer-by-Layer (LBL) method, followed by heating at 100 °C. The electrical conductivity of the cotton using different concentrations of graphene was studied. The graphene-coated cotton, at the 17th layer, with a concentration of 168.36 wt.% resulted in a surface resistance of 0.644 Ω/sq and retained the maximum resistance even after two months. Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectroscopy analysis (EDX) were employed to comprehend the surface morphology and elemental compositions. Fourier transform infrared (FTIR) spectroscopy, UV-vis absorption, and X-ray diffraction (XRD) were used to determine the structural analysis, which revealed a good dispersion of graphene in the cotton samples obtained through dimethyl sulfoxide (DMSO) doping, which reduced the ripple of the cotton. The cotton fabric treated with graphene was thermally stable, as shown through thermal analysis. From the results obtained, it is evident that graphene-treated cotton fabric materials show tremendous potential for use in smart textiles and also as protective clothing.