This paper is concerned with the preparation of a silica gel–carbon black composite by the sol–gel process, which consists of tetraethoxysilane and polymer-grafted carbon black. Polymer-grafted carbon black was synthesized by three methods: (1) cationic polymerization of N-vinyl-2-pyrrolidone, (2) cationic ring-opening polymerization of 2-methyl-2-oxazoline, and (3) radical polymerization of glycidyl methacrylate followed by reaction of glycidyl groups in the grafted polymer chains with 3-aminopropyltriethoxysilane. The polycondensation of tetraethoxysilane proceeded under acidic conditions in the presence of polymer-grafted carbon black to give a deep black silica gel–carbon black composite. The more the content of untreated carbon black was increased, the more the gelation time was shortened. On the contrary, gelation was retarded by grafted polymer chains on the carbon black surface in the case of polymer-grafted carbon black. The scratch hardness of the resulting silica gel–carbon black composite was almost equal regardless of the carbon black content in the presence of untreated carbon black, whereas it was liable to decrease as the content of polymer-grafted carbon black increased. The solvent adsorption properties of the silica gel–polymer-grafted carbon black composite varied with the solubility of grafted polymer chains on the carbon black surface towards the immersion solvent.