Amino-terminated poly(2-methyl-2-oxazoline) (PMeOXz-NH2) was synthesized using the living cationic ring-opening polymerization of 2-methyl-2-oxazoline (MeOXz). PMeOXz chains were introduced onto graphene oxide (GO) by the condensation reaction between GO and PMeOXz-NH2 to give PMeOXz-grafted GO (PMeOXz-g-GO), which was converted to PMeOXz-grafted reduced graphene oxide (PMeOXz-g-rGO) by hydrazine reduction. Acid-catalyzed sol-gel method of tetraethoxysilane was carried out in the presence of PMeOXz-g-rGO to give a transparent PMeOXz-g-rGO/SiO2 hybrid retaining the optical property of rGO.