Block copolymers are polymers whose molecular chains consist of incompatible segments that can self-assemble to form separated phases or microdomains. The versatile properties of block copolymers are determined by their phase-separated microdomains, generating a variety of applications in biomedical materials, engineering thermoplastics and elastomers, and optical and electrical materials. This invention is directed to a novel method of assembling and controlling the properties of block copolymers. By modifying the surfaces of nanoscale fillers, this method can either chemically tether the block copolymers onto the nanofillers, or otherwise control their interactions, which direct the self-assembly of the phase-separated microdomains, and thus control the overall properties of the block copolymers.