New polymer composites containing polyaniline‐carboxymethyl cellulose (PANI‐CMC) were prepared via the polymerization of aniline hydrochloride using different concentration (wt%) of sodium CMC using ammonium persulfate as an oxidant. The thermal stability and embedded crystallinity of the composites were investigated using thermogravimetric and X‐ray diffraction analysis method, respectively. The electrical properties of the composites were examined using temperature‐dependent DC conductivity within 300–500 K. As compared to pure polyaniline the composites with increasing CMC in the PANI‐CMC composites shows the enhancement in the higher crystallinity and thermal stability, and higher electrical conductivities under equivalent conditions. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers