The synthesis and properties of two semiconducting donor-acceptor (D-A) block copolymers and their application in nanostructured bulk heterojunction solar cells are reported. The donor segments were obtained via nitroxide mediated polymerization of either bis(4-methoxyphenyl)-4'-vinylphenylamine or N,N'-bis(4-methoxyphenyl)-N-phenyl-N'-4-vinylphenyl-[1,1'biphenyl]-4,4'-diamine. Narrow-distributed macroinitiators, poly{bis(4-methoxyphenyl)-4'-vinylphenylamine} (PvDMTPA) and poly{N,N'-bis(4-methoxyphenyl)- N-phenyl-N'-4-vinylphenyl-[1,1'biphenyl]-4,4'-diamine} (PvDMTPD) were used to polymerize the acceptor monomer perylene diimide acrylate (PerAcr) to yield block copolymers with well-defined molecular weights. Different diblock copolymers, PvDMTPA-block-PPerAcr and PvDMTPD-block-PPerAcr, with high perylene diimide weight fractions were prepared. The block copolymers exhibited efficient fluorescence quenching. Transmission electron microscopy revealed wire-like and worm-like nanostructures throughout bulk samples. Thin film photovoltaic devices showed short circuit currents J(SC) of up to 1.21 mA/cm(2) and power conversion efficiencies eta of 0.32% under AM 1.5 illumination conditions.