We present a new approach to achieving order in molecular semiconductors via alignment of polymer chains using surface-initiated polymerization. Polyacrylate brushes grown from transparent conducting electrodes, with triarylamine side groups as hole-transporting components, show characteristics of high mobilities for hole transport. Solution processing a second component with favorable enthalpic interactions can form a composite with mesoscale order and be exploited for heterojunction diodes. We find substantial uptake of CdSe nanocrystals (with diameter in the range 2.5-2.8 nm), and such composites show photovoltaic quantum efficiencies of up to 50%.