We report a photophysical study of photovoltaic blends containing perylene-substituted polyisocyanide (pery-PIC) materials, using time-correlated single photon counting (TCSPC) and photo-induced absorption spectroscopy, and compare the key characteristics to analogous perylene-diimide (PDI) monomer blends with polythiophene-and polyfluorene-based conjugated polymers. Pery-PIC consists of semiconducting perylene units, which self-stack in a regular fashion around a rigid helical poly-isocyanopeptide backbone. In particular, the charged state lifetimes in pery-PIC blends are found to be of order 10s of μs; this being typically less than half those of the perylene-anion in the corresponding PDI blends. We consider the influence of photophysical factors on the superior photovoltaic device performance of the pery-PIC blends, relative to the corresponding PDI-based devices, in addition to the morphological effects described in earlier studies.