Photoinduced charge separation, charge recombination, and trapping in polymer blend organic photovoltaic materials are examined using ultrafast 2D IR and vis-IR spectroscopy in conjunction with transient photocurrent techniques. Native vibrational modes of the functionalized fullerene, PCBM, are probed as reporters of the charge carrier dynamics. Following a free carrier formation process that occurs on a surprisingly fast picosecond time scale, charge carriers become trapped in poly(p-phenylenevinylene) (PPV)-based OPV materials but are not readily trapped in polythiophene (PT)-based materials. The trapping process results in the formation of distinct vibrational features that are not present in the PT-based materials. Although the origin of the distinct trapping characteristics remains unclear, they help rationalize the qualitatively different bimolecular charge recombination behavior that has been observed in PPV-based versus PT-based OPV materials. 2D IR spectroelectrochemical investigations of trapped charges may provide a means to elucidate the structures of the traps in PPV-based materials.