Polypyrrole (PPy) nanomaterials have been synthesized with varying concentrations (10–40 mM) of anionic surfactant camphor sulphonic acid (CSA) using the chemical polymerization method, and then utilized for electromagnetic interference (EMI) shielding applications in the X-band of the microwave frequency range (8.2–12.4 GHz). An observable systematic change in the morphology of the prepared PPy has been noted, with highly aggregated globules transforming into fibular-like structures with an average diameter of approximately 80–120 nm as the CSA concentration increased. Raman and Fourier-transform infrared (FTIR) measurements indicate an increase in the relative intensities of the bipolaronic to polaronic bands, suggesting an improved conjugation of PPy with increasing CSA concentration. The electrical conductivity at room temperature has also been found to increase significantly, from 2.55 S/cm to 35.80 S/cm, as the concentration of CSA surfactant increased from 10 mM to 40 mM. Additionally, the shielding effectiveness (SE) for reflection (SE R ), SE for absorption (SE A ), and total SE (SE T ) have been found to increase with increasing CSA concentration in PPy. The SE T values have been found exceeding 35 dB throughout the X-band of the microwave region in PPy nanomaterials with CSA concentrations ≥ 20 mM. It has been observed that CSA-directed polypyrrole exhibits high electrical conductivity, where the SE for absorption (SE A ) dominates over the SE for reflection (SE R ). This study suggests that the properties of PPy can be easily tailored for its potential utilization in the fabrication of various EMI shielding devices with improved performance.