Integration of regioregular poly(3-hexylthiophene) in diblock copolymers with various poly (methacrylates) yielded electronic materials with variable conductivities and different types of nanoscale order. Solid state analysis of poly(3-hexylthiophene)-block-poly(methyl methacrylate) and poly(3 -hexylthiophene)-block-poly(t-butyl methacrylate) diblock copolymers revealed the presence of densely packed, locally parallel nanofibrils. By contrast, poly hexylthiophene)-block-poly(isobornyl methacrylate) copolymers containing bulkier isobornyl functional groups exhibited nanofibrillar morphology with isolated fibrils and no interfibrillar order.