The formation of mobile charges in a roll-to-roll processed poly-3-hexylthiophene-fullerene bulk heterojunction film is observed directly by using transient terahertz spectroscopy with sub-100 fs temporal resolution. The transient terahertz ac conductivity reveals that 20% of the incident pump photons are converted into highly delocalized charges within the 40 fs, 3.1 eV pump pulse duration, which then rapidly becomes localized within 120 fs. Approximately 2/3 of these carriers subsequently decay, possibly into an exciton, on a 1 ps time scale.