In the quest for better power conversion efficiency of organic photovoltaic cells (OPVC) various architectures have been considered. Bulk heterojunction type OPVC proved to be the most successful, where the polymer as electron donor is blended with fullerene molecule as electron acceptor. With the goal of improving power conversion efficiency of OPVC we studied 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM) as a film and dispersed in polystyrene matrix. We used a variety of continuous wave (cw) optical probes including photoinduced absorption (PA), photoluminescence (PL), and optically detected magnetic resonance (ODMR). The steady state photophysics of PCBM is dominated by triplet exciton. For both PCBM dispersed in polystyrene and PCBM film, the triplet exciton specie is characterized by a PA band at about 1.7 eV and spin 1 PA detected magnetic resonance (PADMR) powder pattern resonance around g ∼ 2. However, in PCBM film the occurrence of a polaron PA band at 1.2 eV and spin 1/2 PADMR are also noticed.