The conducting polymer, polyaniline (PANI), was synthesized in its emeraldine salt (ES) and emeraldine base (EB) forms by the method of chemical oxidative polymerization using hydrochloric acid (HCl) as the dopant. Characterization of these samples was carried out by UV–Visible spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive X-ray Spectroscopy (EDX) and two probe conductivity measurements. It was observed that the electrical conductivity of the ES form of PANI had a six-order increase when compared to its EB form. This result was correlated with the morphological switch-over from granular to coral-reef structure of the PANI. Optical properties of the two forms were compared using Tauc plots and Urbach tail analyses. This article emphasizes a thorough investigation of the relatable features of the ES and EB forms of PANI toward tuning its d.c. conductivity. The study places a strong emphasis on the use of characterization techniques as an effective tool for characterizing the electrical properties of PANI. The tailoring of these properties of the two forms of PANI can empower the applicability of this class of conducting polymers in various state-of-the art devices.