p-Toluene Sulphonic Acid (PTSA) doped polyaniline (PANI) analogues were synthesized by oxidative chemical polymerization method and characterized by TGA FTIR and EPR spectroscopic techniques. FTIR spectra indicates the formation of PTSA doped PANI and also revealed the dopant ions mediated interactions between polymeric chain through weak hydrogen bonding. TGA plots revealed that there is systematic variation in the weight loss at ∼300 °C from ∼4% to ∼38% with increase in dopant concentration from 0.01 N to 1.0 N. Magnetic resonance spectra of polaron charge carriers exhibit the single Lorentzian line signal with the Dysonian contribution indicating formation of metal-like domains. The polarons are localized in these domains by strong interaction between the neighboring conducting chains, in which the charge is transferred by quasi-three-dimensional (Q3D) delocalized electron. In higher concentration analogue some of polarons merge into diamagnetic bipolarons and this reduces intensity of EPR signal. The electrical conductivity of the 1.0 N PTSA doped sample was ∼4.5 S/cm which satisfies the EMI shielding criteri.