A novel nano-biocomposite of silver and poly(o-methoxy aniline) (POMA)/DNA hybrid has been prepared by adding DNA solution to an aqueous solution of POMA (emeraldine base, EB) and AgNO(3) mixture. The mixture was aged for 10 days and was freeze-dried to form the hybrid nanocomposite (weight fraction of DNA = 0.75). FESEM pictures show a fibrillar network morphology of the biomolecular hybrid with silver nanoparticles on its surface. The TEM picture also corroborates silver nanoparticle formation in the biomolecular hybrid, and the denser population of nanoparticles in the TEM micrograph as compared to that in the SEM micrograph indicates that the nanoparticles are present inside the fibrils in greater proportion. The dc conductivity value of the hybrid indicates that POMA (EB) is doped by silver ion and the doped POMA form complexes with DNA through electrostatic interaction of the radical cation of POMA (emeraldine salt form, ES) and the DNA anion. During the doping process and Ag nanoparticle formation, a fluctuation of the pi band to polaron band transition peak occurs together with a complementary fluctuation of the polaron band to pi* band transition peak. After 53 h of aging, the former shows a slow but continuous red shift with aging time. This has been attributed to the slow uncoiling of POMA on the DNA surface. The conformation and crystal structure of DNA remain intact during the nano-biocomposite formation. The dc conductivity value of the nano-biocomposite is almost the same as that of the pure POMA-DNA hybrid at the same composition, but the I-V characteristic curve of the nano-biocomposite is somewhat different showing an insulating region on low applied voltage. At higher applied voltage, it shows a semiconducting property characterizing the large band gap semiconducting behavior of the nano-biocomposite.