This thesis presents a study of photo-active, semiconducting block copolymers for use in molecular solar cells. Current state-of-the-art organic devices utilise blends of two (or more) materials that are co-deposited from a common solution; the resulting structures formed are determined by material properties and deposition conditions, but often result in configurations that are detrimental to device performance. An answer to this problem comes in the form of the block copolymer; using these materials, devices can be formed from a single material active layer. In addition, the counterbalance of forces within films of block copolymer can lead to nano-scale self-assembly that allows for a strong degree of control over layer equilibrium morphology. Such control will be an important step forward in the evolution of molecular solar cells. The main body of this work is concerned with the study of the photo-physics of photo-conductive block copolymers, especially the generation of free charge. First, an investigation is made into the inherent structure-function relationship in block copolymers. A varying chain length is seen to drastically affect the photoluminescence quenching and yield of long-lived charges. Photovoltaic devices made using these materials show a peak efficiency of 0.11% and correlate with the spectroscopic results, subject to a trade off between charge generation and transport/collection. In a second investigation, the effects of post-fabrication annealing on block copolymer films are considered; studies on annealed samples lead to the conclusion that domain crystallinity is a significant factor in determining the yields of long-lived charge carriers. It is found that these yields are comparable with those of a standard blend (that achieve 75% photon to electron conversion efficiency). Annealing leads to increases in photovoltaic device performance over unannealed samples, although additional control over active layer morphology is necessary for these materials to attain their potential. Following this, a comparative study is made between a block copolymer and a similarly composed blend formed from well studied polyfluorene copolymers. Further advantages of block copolymers are highlighted, including the stability of morphologies generated under different deposition conditions. Finally, a novel tool set is introduced using a block copolymer sample to emphasise the experiments potential with regard to studying interfacial photophysical effects.