Thin films composed of polycyclohexane (PCHE), zinc(II)-5,10,15,20-tetra-(2-naphthyl)porphyrin (ZnTNpP), and [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) blends are prepared to investigate their potential for the controlled self-assembly of a porphyrin/fullerene donor-acceptor complex in a polymer thin film. The compatibilities of PCHE/PCBM (p), PCHE/ZnTNpP (q), and ZnTNpP/PCBM (r) in these blends have a significant effect on the dispersion of the ZnTNpP/PCBM donor-acceptor complex in the PCHE thin film. When the compatibilities are p << q, r, and q approximate to r, the ZnTNpP/PCBM donor-acceptor complex is formed between the PCHE and PCBM phases. This concept to form a controlled self-assembly of the ZnTNpP/PCBM donor-acceptor complex may be applied to various combinations of porphyrin/fullerene systems in polymer thin film solar cells to achieve excellent performance. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 743-746