This research is devoted to a comprehensive analysis of the structural, dielectric, and electro-optic modifications of the nematic liquid crystal 4-cyano-4’-pentylbiphenyl (5CB) upon the incorporation of silver (Ag) nanoparticles. The primary aim of the study is to investigate how silver nanostructures (approximately 20–80 nm in size) alter the fundamental properties of the 5CB medium, and to compare the obtained results with those arising from the influence of other metals. The main focus of the work is on changes in dielectric anisotropy (∆ε). It has been established that the addition of silver nanoparticles at relatively low concentrations (around 0.5–1%) leads to significant modifications in key parameters such as dielectric permittivity and dielectric losses of 5CB. The distinctive distribution of silver within the 4-cyano- 4’-pentylbiphenyl matrix plays a decisive role in controlling the system’s conductivity. Comparative analyses demonstrate that silver-doped composite materials exhibitenhanced electro-optic sensitivity, which distinguishes them from composites doped with other metals.