The use of chlorotricarbonyl rhenium(I) diimine complex as photosensitizing molecule in photovoltaic cells is demonstrated. Unlike other transition-metal-based sensitizers, the complex is sublimable and has low band gap. It also exhibits bipolar charge transport character with relatively high carrier mobilities on the order of 10(-3) cm(2) V-1 s(-1). Multilayer heterojunction and bulk heterojunction devices with fullerene as the electron accepting molecule were prepared. For the bulk heterojunction devices, the fill factor and power conversion efficiency under simulated solar light illumination were 0.56 and 0.48%, respectively. Atomic force microscopic images showed that the complex dispersed evenly with fullerene molecules in solid state. (C) 2004 American Institute of Physics.