Polymer-fullerene blend films are of increasing interest in the field of organic solar cells. This thesis describes the use of transient absorption spectroscopy (TAS) as a means to study charge generation and recombination in these blend films. In blend films of P3HT and PCBM, the absorption spectrum associated with the positive and negative charges have been identified and the transient decay kinetics analysed to reveal the mechanisms leading to charge recombination losses in the films. The effects of annealing treatment, along with the effects of decreasing polymer regioregularity or different polymer chain terminating end-groups on the blend film properties and morphology are also discussed. For films with a low concentration of PCBM in polystyrene, absorption and emission from the individual PCBM molecules are observed. As the PCBM concentration is increased, aggregation related changes causes the absorption in the visible region to increase disproportionately, an additional emission peak at higher energies to appear and a decrease in the lifetime of the PCBM triplet excited state. These changes are linked to electronic interactions between fullerenes in a molecular crystal form of PCBM. Blends of F8BT polymer with PCBM show poor photovoltaic device performance. This is explained by the quick deactivation of the F8BT excited state by Förster energy transfer to the PCBM. As the PCBM excited state is stable compared to the charge separated state, the PCBM triplet is formed via inter-system crossing from the singlet to be the final product of photoexcitation. The high energy of the charge separated state is interpreted as a result of the high F8BT HOMO energy.