The dielectric investigations of porous synthetic silica gel modified with polyaniline (PANI) and polyethylene glycol (PEG) polyblend at various concentrations are demonstrated in this paper. By using the chemical oxidative process to embed polyaniline (PANI) and polyethylene glycol (PEG) into a silica matrix, conducting gel nanocomposites were synthesized. For various dopant concentrations, the dielectric permittivity (ε′), D.C. conductivity (σdc), loss tangent (tanδ) and dielectric loss (ε″) were investigated. The samples were characterized using differential thermal analysis/thermogravimetric analysis, Fourier transform infrared spectroscopy and high‐resolution transmission electron microscopy. Depending on the co‐blend content, PANI‐PEG modified silica structures produce nanoparticles ranging in size from 9.9 to 48.1 nm. The variation of DC conductivity (σdc) with PANI/PEG content shows Maxwell‐Wagner Sillars (MWS) effect confirming the role of the conjugation and the structural order.