We report on the synthesis of an electrically conductive chitosan nanofibrous scaffold (NFS) by a "simple template free self-assembly method" from biopolymer chitosan in the presence of inorganic acids as dopants and ammonium persulphate (APS) as an initiator. The morphology of the chitosan nanofibers scaffold (CS-NFS) was examined by field emission scanning electron microscopy (FE-SEM). Physiochemical characterizations of the CS-NFS were analyzed by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis. It is found that the morphology and structure of the CS-NFS strongly depend on the kinds of dopant used. Cyclic voltammogram measurement reveals that CS nanofibers have high electrocatalytic activity compared to chitosan powder. The CS nanofibers are expected to be useful in electrical, optical, and electrochemical devices.