© 2014 American Chemical Society. A benzannulated boron dipyrromethene (BODIPY, bDIP) molecule exhibiting strong absorption at 640 nm was synthesized. The organic dye was used in an organic solar cell as the electron donor with C60 as the acceptor. The BODIPY dye demonstrated the best performance in lamellar architecture (indium tin oxide (ITO)/bDIP/C60/bathocuproine/Al), giving power conversion efficiency up to 4.5% with short-circuit current (JSC) of 8.7 mA/cm2 and an open-circuit voltage (VOC) of 0.81 V. Neutron reflectivity experiments were performed on the bilayer film to investigate the thickness dependence of JSC. A 13 nm mixed layer was found to be present at the donor/acceptor interface in the bilayer device, formed when the C60 was deposited onto a room temperature bDIP film. Planar-mixed heterojunction devices were fabricated to understand the extent of spontaneous mixing between the donor and acceptor materials. The native mixed region in the bilayer device was shown to most resemble 1:3 bDIP:C60 layer in the structure: (ITO/bDIP/bDIP:C60 blend/C60/bathocuproine/Al).