Summary: Silica gel, an important inorganic polymer with many applications, was silylated with 3‐(phenylaminopropyl)trimethoxysilane (PAPTMOS) by means of a novel “low solvent” method, whereby the silane was dissolved in a small amount of methanol, mixed with silica and reaction carried out in a heated vacuum oven. Polyaniline (PANI) was grafted to the silylated silica by in situ polymerization of aniline, then dedoped with aqueous ammonia. Physically adsorbed PANI was removed from the modified silica by washing with tetrahydrofuran (THF) and N‐methyl‐2‐pyrrolidone (NMP). The silylated, PANI‐modified silica had electrical conductivity 1.2 × 10−3 S cm−1 after being re‐doped with methanesulfonic acid. FTIR, elemental analysis, X‐ray photoelectron spectroscopy, solid‐state 13C and 29Si NMR and morphological studies by SEM confirmed successful formation of the SiO2‐polyaniline hybrid material.