Opto-electronically active organic polymer materials offer several advantages over traditional solid-state semiconductors in the fabrication of devices such as solar cells and light emitting diodes, including their low cost, low weight, and flexibility. Here, we present the results of ongoing combined theoretical and experimental analytical studies of a block copolymer consisting of a covalently bound polythiophene donor and fullerene acceptor, with the goal of developing a fundamental, systematic, atomistic-scale understanding of the origin of specific optoelectronic properties in order to facilitate the enhancement of the efficiency and functionality of these materials. The electronic structure and transport properties of both the full polymer chains and the individual components were investigated using ab initio density functional theory (DFT) and non-equilibrium Green function calculations. The molecular components were then deposited on metallic surfaces for study using scanning tunnelling microscopy, in conjunction with DFT simulations of the density of states and investigations of the interaction with the substrate.