Direct charge transfer at wet-processed organic/organic heterojunction interfaces is observed using femtosecond interfacial sensitive spectroscopy. UV-vis absorption and ultraviolet photoelectron spectroscopy both indicate that a new interfacial energy gap (∼1.2 eV) exists when an interface is formed between regioregular poly(3-hexylthiophene-2,5-diyl) and poly(benzimidazobenzophenanthroline). Resonant pumping at 1.2 eV creates an electric field-induced second-order optical signal, suggesting the existence of a transient electric field due to separated electrons and holes at interfaces, which recombine through a nongeminate process. The fact that direct charge transfer exists at wet-processed organic/organic heterojunctions provides a physical foundation for the previously reported ground-state charge transfer phenomenon. Also, it creates new opportunities to better control charge transfer with preserved momentum and spins at organic material interfaces for spintronic applications.