A short, simple, versatile methodology was developed for the synthesis of poly(2,5-benzophenone) containing coil−rod−coil triblock copolymers. After a model study, poly(2,5-benzophenone) macroinitiators were synthesized via end-capping poly(2,5-dichlorobenzophenone) synthesized by Ni(0)-catalyzed polymerization and functionalization of the chain ends utilizing phase transfer chlorination. Varying molecular weights of polystyrene-b-poly(2,5-benzophenone)-b-polystyrene were synthesized using the macroinitiators in the atom transfer radical polymerization of styrene. The materials were characterized by gel permeation chromatography, nuclear magnetic resonance, differential scanning calorimetry, and transmission electron microscopy. Applications were explored through dynamic mechanical analysis and the construction of a distributed junction photovoltaic device.