PANI-LiCl was synthesized by chemical oxidative method by varying LiCl concentration. Existence of codopant LiCl was confirmed by XPS and DSC studies. DSC shows that PANI exhibits two peaks, whereas PANI-LiCl show three endothermic peaks. Maximum electrical conductivity 25.01 S cm−1 was realized for 2.5 M LiCl doped PANI.