This tutorial review covers recent contributions in the area of linear π-conjugated systems bound to fullerenes in view of their application as active materials in photovoltaic devices. The first part discusses the concepts of double-cable polymer and molecular hetero-junction and presents several examples of chemically or electrochemically synthesized C₆₀-derivatized conjugated polymers. The second and main part of the article concerns the various classes of C₆₀-derivatized π-conjugated oligomers designed in view of their utilization in single-component photovoltaic devices. Thus, C₆₀-containing π-conjugated systems such as oligoarylenevinylenes, oligoaryleneethynylenes and oligothiophenes are discussed on the basis of the relationships between molecular structure, photophysical properties and performances of the derived photovoltaic devices. A brief last section presents some recent examples of surface-attached molecular hetero-junctions based on self-assembled monolayers and discusses possible routes for future research.