Ag@polycarbazole as a new 3D nanocomposite material was successfully fabricated using microwave polyol reduction method followed by cations assisted oxidative polymerization of carbazole. The material was characterized by transmission electron microscopes (TEM), scanning electron microscope (SEM), FT-IR, and Raman measurements. The results confirmed that Ag nanoparticles are entirely enclosed by 3,6 polycarbazole. The interfacial study was carried out by X-ray photoelectron spectroscopy, which revealed that Ag surface atoms are intact chemically and blue shifted due to polymer composite formation. The surface plasmon resonance (SPR) and photoluminescence (PL) behavior were found quite sensitive to surface composition of Ag nanoparticles, which is greatly influenced by cations dopant and enclosing polymer in contrary way. The polycarbazole played a contributive role to counterbalance the effect of cations dopant in SPR and PL behaviors along with displaying its luminescence in violet region.