Thin films of a tetraphenylporphyrin-end-functionalized polycyclohexane zinc complex (ZnTPP-PCHE)/fullerene-C60 (C60) end-functionalized poly(4-diphenylaminostyrene) (C60-PDAS) were prepared to investigate their potential as a light-harvesting system for polymer solar cells (PSCs). The microphase separation in the ZnTPP-PCHE/C60-PDAS blends had a significant effect on the optical properties; the absorption band of the microphase separation structure that overlaps the visible-light region was considerably enhanced with an increase in the C60 concentration in the polymer film, although both pristine ZnTPP-PCHE and C60-PDAS thin films had only weak absorption bands in that region. Therefore, this polymer blend is considered to be suitable for use as a light-harvesting system for PSCs. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013