Eco-friendly and economically visible processing routes of nanomaterial and nanocomposite is essentially required for the industrial scaling of nanotechnology. The present work aims to prepare ferroelectric polymer nanocomposites with high permittivity to be useful as high dielectric constant (high-k) materials because of their potential applications in the electronic and electrical industries. Therefore, the semiconducting molybdenum disulfide (MoS2) exfoliated by the one-pot hydrothermal method was introduced at different concentrations into a ferroelectric polyvinylidene fluoride (PVDF) matrix, forming MoS2/PVDF nanocomposite films which were annealed at 160oC for 5 h. Then, the electrical properties of these films were investigated over a wide range of frequencies at room temperature using the broadband dielectric spectrometer (BDS). In addition, the thermal properties of MoS2/PVDF nanocomposite were evaluated. It was found that the samples annealing at 160 oC did not affect the electrical properties but showed electrical stability of all the nanocomposite films. The interfacial polarization and DC conductivity highly affected the samples electrical properties. The composites with high loading of MoS2 nanosheets (>1wt. %) significantly enhanced both of permittivity and electrical conductivity.