This work presents a methodology to develop innovative and durable materials for their potential membrane and templating applications. Towards this goal, we are strategically manipulating the interface between blocks in poly(styrene-b-isoprene) [PS-PI] block copolymers using anionic polymerization techniques. By following this approach, we are able to control the interfacial interactions between blocks independent of molecular weight and block constituents. A library of copolymers is prepared with various interfacial modifications to enable the examination of interfacial effects on copolymer self-assembly. The molecular characteristics of the block copolymers are characterized by gel permeation chromatography (GPC), NMR, and ozonolysis. The morphology of the microphase-separated domain structures is investigated by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA).