We use flash-photolysis time-resolved microwave conductivity experiments (FP-TRMC) and femto-second-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 phthalocyarline (TiOPc), and fullerene (C-60). Carrier generation following selective photoexcitation of TiOPc is independently observed at both the P3HT/TiOPc and TiOPc/C-60 interfaces. The transient absorption results indicate that following initial charge generation processes to produce P3HT(center dot+)/TiOPc center dot- and TiOPc center dot+/C-60(center dot-) at each interface from (P3HT/TiOPc*/C-60, the final charge-separated product of (P3HT(center dot+)/TiOPc/C-60(center dot-)) is responsible for the lont-lived photoconductance signals in FP-TRMC. (A)t the P3HT/TiOPc interface in both P3HT/TiOPc60 the electron transfer appears to occur only with the crystalline (weakly coupled H-aggregate) phase of the P3HT.