Conducting poly(3,4-ethylenedioxythiophene): poly(styrene-4-sulfonate) (PEDOT:PSS) containing hydroxyl surface rich SiO2 nanoparticles were investigated. Rearrangement and bonding of PEDOT: PSS were affected by the content of SiO2 nanoparticles, which resulted in the modification of an electronic band structure and electrical characteristics. A slight decrease in work function and a shift of the highly occupied molecular orbital edge to the Fermi level were induced by SiO2 nanoparticle addition. The current path was also tuned by SiO2 nanoparticles and resistance of the composite film was diminished. SiO2 nanoparticles affect electrostatic bonding between PEDOT: PSS and doping of PEDOT as well as increase the packing density of PEDOT: PSS.