We use flash-photolysis time-resolved microwave conductivity experiments (FP-TRMC) and femtosecond–nanosecond pump–probe transient absorption spectroscopy to investigate photoinduced carrier generation and recombination dynamics of a trilayer cascade heterojunction composed of poly­(3-hexylthiophene) (P3HT), titanyl phthalocyanine (TiOPc), and fullerene (C60). Carrier generation following selective photoexcitation of TiOPc is independently observed at both the P3HT/TiOPc and TiOPc/C60 interfaces. The transient absorption results indicate that following initial charge generation processes to produce P3HT•+/TiOPc•– and TiOPc•+/C60 •– at each interface from (P3HT/TiOPc*/C60), the final charge-separated product of (P3HT•+/TiOPc/C60 •–) is responsible for the long-lived photoconductance signals in FP-TRMC. At the P3HT/TiOPc interface in both P3HT/TiOPc and P3HT/TiOPc/C60 samples, the electron transfer appears to occur only with the crystalline (weakly coupled H-aggregate) phase of the P3HT.