In this work, a benzenedinitrile functionalized monomer, 2-methyl-acrylic acid 6-(3,4-dicyano-phenoxy)-hexyl ester, was successfully polymerized via the reversible addition-fragmentation chain transfer method. The polymerization behavior conveyed the characteristics of “living”/controlled radical polymerization: the first-order kinetics, linear increase of number-average molecular weight with monomer conversion, narrow molecular weight distribution, and successful chain-extension experiment. The soluble Zn(II) phthalocyanine (Pc)-containing (ZnPc) polymers were achieved by post-polymerization modification of the obtained polymers. The Zn(II) phthalocyanine-functionalized polymer was characterized by FTIR, UV–vis, fluorescence, atomic absorption spectroscopy, and thermogravimetric analysis. The potential application of above ZnPc-functionalized polymer as electron donor material in bulk heterojunction organic solar cell was studied. The device with ITO/PEDOT:PSS/ZnPc-Polymer/PC61BM/LiF/Al structure provided a power conversion efficiency of 0.014%, fill factor of 0.24, open circuit voltage (Voc) of 0.21 V, and short-circuit current (Jsc) of 0.28 mA/cm2. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 691–698