In present work, spherical core (polystyrene, PS)/shell (polypyrrole, PPy) has been synthesized via in situ chemical oxidative copolymerization of pyrrole (Py) on the surface of sulfonated PS microsphere followed by the formation of hollow polypyrrole (HPPy) shell by dissolving PS inner core in THF. Thereafter, we first time established that such fabricated novel art of morphology acts as a conducting trap in absorbing electromagnetic (EM) wave by internal reflection. Further studies have been extended on the formation of its silver nanocomposites HPPy/Ag to strengthen our contention on this novel approach. Our investigations showed that electromagnetic interference (EMI) shielding efficiency (SE) of HPPy (34.5-6 dB) is significantly higher compared to PPy (20-5 dB) in the frequency range of 0.5-8 GHz due to the trapping of EM wave by internal reflection. We also observed that EMI shielding is further enhanced to 59-23 in 10 wt% Ag loaded HPPy/Ag-10. This is attributed to the simultaneous contribution of internal reflection as well as reflection from outer surface. Such high EMI shielding capacity using conducting polymers are rarely reported.