Thin films composed of zinc tetraphenylporphyrin-end-functionalized polycyclohexane (ZnTPP-PCHE) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blends were prepared to investigate their potential as light-harvesting systems within polymer solar cells (PSCs). Both the microphase separation characteristics and the extent of pp interactions in these ZnTPP-PCHE/PCBM blends had significant effects on the optical properties of the films. The extent to which the absorption bands of the films overlapped the terrestrial solar spectrum was increased considerably when the blends formed a co-continuous structure, even though films of pure ZnTPP-PCHE or PCBM exhibited only weak absorption over that wavelength region. We conclude that these polymer blend films may be considered as viable candidates for light-harvesting systems within PSCs. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013