The present work describes the dual role of graphene as an initiator and filler for polymerization of N vinylcarbazole and formation of poly(N-vinylcarbazole)/graphene (PVK/Gr) nanocomposites. Fourier transformation infrared (FTIR) and X-ray diffraction (XRD) studies confirmed the formation of PVK as well its graphene nanocomposites. Scanning electron micrograph (SEM) and transmission electron microscopy (TEM) revealed the graphene platelets are dispersed in the matrix of spherical PVK. X-ray photoelectron spectroscopy (XPS) also revealed formation of PVK and presence of interaction between PVK and graphene. Thermograivmetric analysis (TGA) have shown that the thermal stability of PVK/graphene (0.5 wt%) is maximum improved by ∼76 °C compared to neat PVK, when 20 wt% weight loss is taken as a point of comparison. Ultraviolet (UV) and photoluminescence (PL) studies established the charge transfer from polymer chains to the graphene platelets. Dielectric measurements have shown the maximum improvement (87%) in dielectric constant (ε) with 1 wt% graphene loading. The variation of ac conductivity (σ) with frequency (ω) confirmed the insulating behavior of PVK/graphene nanocomposites possessing high dielectric constant.