PBDTTPD is one of the best conjugated polymers for solar cell applications (up to 8.5% efficiency). We have investigated the dynamics of charge generation in the blend with fullerene (PCBM) and addressed highly relevant topics such as the role of bulk heterojunction structure, fullerene excitation, and excess energy. We show that there are multiple charge separation pathways. These include electron transfer from photoexcited polymer, hole transfer from photoexcited PCBM, prompt (