Synthesis of RNA-templated Ag/PVA nanobiocomposites of controlled morphology was investigated. Surface morphologies of the composites and size distributions of the nanofillers were analyzed by means of field emission scanning electron microscopy. Interfacial interaction between the different components was followed by monitoring the surface plasmon resonance of silver nanoparticles in nanobiocomposites. The band gap approximations suggested semiconducting behavior of the nanobiocomposites with larger band gap than that of the conventional semiconductors. RNA-stabilized Ag/PVA nanobiocomposites revealed the presence of well-dispersed and spherical Ag nanoparticles in PVA matrix with a size distribution of 14–23 nm. IR spectra of the nanobiocomposites demonstrated the complex behavior of RNA with Ag nanoparticles in the polymer matrix due to the presence of noncovalent interactions (electrostatic/van der Waals) between RNA, Ag, and PVA molecules. The effects of the loading of RNA-capped Ag nanoparticles on the electrical properties of PVA were also observed by analyzing I–V characteristics of nanobiocomposites which displayed a large increase (≈89 %) at low concentration relative to neat PVA. The drastic improvement in optical and electrical properties of the nanobiocomposites indicated their promising applications in nanobiotechnology.