Poly(oxyethylene methacrylate) (POEM) anchored TiO2 nanoparticles were synthesized via the surface thiol-lactam initiated radical polymerization of POEM in the presence of thiol functionalized TiO2 nanoparticles. The grafting of POEM onto the surface of TiO2 nanoparticles was investigated by FT-IR, XPS, EDX, TGA, XRD, and TEM analyses. The experimental findings suggested that a strong interaction prevailed between grafted POEM and TiO2 nanoparticles. The TEM image of POEM-g-TiO2 showed that the agglomeration propensity of TiO2 nanoparticles was reduced significantly upon the functionalization of POEM. Moreover, an improved thermal property of the POEM in the POEM-g-TiO2 nanocomposites was observed by TGA.