Straightforward synthetic methodologies are reported for the functionalization of oligothiophenes with hydrogen-bonding motifs. Codeposition from a solution of symmetric melamine-terminated electron-donor oligomers with a complementary barbiturate-labeled electron-acceptor fullerene resulted in homogeneous films. Incorporation into photovoltaic devices gave a 2.5-fold enhancement in light energy to electrical energy conversion when compared to analogous systems with the non-hydrogen-bonding parent C(60). [reaction: see text]